Cathode slurry for secondary battery

ABSTRACT

A cathode slurry comprises a cathode active material, especially a nickel-containing cathode active material, a binder, a solvent and a base having a formula of R 1 R 2 R 3 N, with improved stability in water. Pre-treatment of nickel-containing cathode active materials may improve stability of the cathode by preventing undesirable decomposition of the material. In addition, battery cells comprising the cathode prepared by the cathode slurry exhibit impressive electrochemical performances.

FIELD OF THE INVENTION

The present invention relates to the field of batteries. In particular,this invention relates to cathode slurries for lithium-ion batteries.

BACKGROUND OF THE INVENTION

Over the past decades, lithium-ion batteries (LIBs) have become to bewidely utilized in various applications, especially consumerelectronics, because of their outstanding energy density, long cyclelife and high discharging capability. Due to rapid market development ofelectric vehicles (EV) and grid energy storage, high-performance,low-cost LIBs are currently offering one of the most promising optionsfor large-scale energy storage devices.

The use of multi-element lithium transition metal oxide such as lithiumnickel manganese cobalt oxide (NMC) and lithium nickel cobalt aluminumoxide (NCA) has become popular due to their superior electrochemicalproperties over traditional cathode active material such as LiMnO₂,LiCoO₂, and LiNiO₂. Such superior electrochemical properties include ahigh energy density and superior capacity performance.

Currently, cathodes are often prepared by dispersing a cathode activematerial, binder material and conductive agent in an organic solventsuch as N-methyl-2-pyrrolidone (NMP) to form a cathode slurry, thencoating the cathode slurry onto a current collector and drying it.

The use of aqueous solutions instead of organic solvents is preferredfor environmental reasons and easier handling and therefore water-basedslurries have been considered. However, nickel-containing cathode activematerials can react with water during electrode preparation, whichcauses metals in the cathode active material to leach out of the cathodeactive material and leads to performance degradation. Lithiumdissolution at the surface of the cathode active material results in theformation of soluble bases. The high soluble base content raises the pHof the cathode slurry, which may affect dispersion homogeneity of thecomponents (e.g., cathode active material) in the cathode slurry andbinding strength of the binder material. It can also have negativeeffects on the metallic components of the electrode (e.g., the currentcollector) and adversely affects the performance of the cathode activematerial. For example, the cathode active material will react withaluminum foil current collectors to produce Al(OH)₃ precipitate, whichwill hinder the transfer of lithium ions, thereby reducing the batterycapacity retention rate. These factors all contribute to poorelectrochemical performance. Conventionally, a pH modifier is used toadjust the pH of the cathode slurry. However, such additives may alsohave a deleterious effect on the electrochemical processes that takeplace at the cathode, especially at higher voltages and temperatures,which in turn diminishes battery performance. Accordingly, it isdesirable to prevent lithium dissolution from the surface of the cathodeactive material in the process of the cathode slurry preparation.

EP Patent Application Publication No. 3044822 A discloses a water-basedlithium transition metal oxide cathode slurry. The slurry comprises alithium transition metal oxide powder, which consists of primaryparticles comprising a polymer-containing coating layer. The coatinglayer is composed of two layers. The outer layer contains afluorine-containing polymer that prevents the pH-raising ion exchangereaction with water by reducing surface coverage of water. The innerlayer contains a product, such as LiF, of the reaction between thepolymer of the outer layer and the lithium transition metal oxide, wherethe reaction decomposes the surface base and reduces the base potentialof the oxide. However, the fluorine-containing polymers increaseelectrical resistance, which leads to reduced battery performance, aswell as pose risks to the health of people and the environment.

In view of the above, there is always a need to develop a method forpreparing cathode slurries having a nickel-containing cathode activematerial for lithium-ion batteries with good electrochemical performanceusing a simple, fast and environmentally-friendly method.

SUMMARY OF THE INVENTION

The aforementioned needs are met by various aspects and embodimentsdisclosed herein. Provided herein is a cathode slurry for a secondarybattery, comprising a cathode active material, a binder, a solvent and abase having a formula of R¹R²R³N, wherein each of R¹, R² and R³ isindependently H, C₁₋₆ alkyl, C₃₋₆ cycloalkyl, C₁₋₆ heteroalkyl, C₄₋₆cycloalkylalkyl, C₂₋₆ alkoxyalkyl, or C₃₋₆ alkoxyalkoxyalkyl, where theC₁₋₆ alkyl, C₃₋₆ cycloalkyl, C₁₋₆ heteroalkyl, C₄₋₆ cycloalkylalkyl,C₂₋₆ alkoxyalkyl, or C₃₋₆ alkoxyalkoxyalkyl is optionally substitutedwith one or more substituents, where each of the substituents isindependently alkyl or cycloalkyl.

In some embodiments, each of R¹, R² and R³ is independently C₁₋₄ alkyl,C₃₋₅ cycloalkyl, C₁₋₄ heteroalkyl, C₂₋₄ alkoxyalkyl, or C₃₋₅alkoxyalkoxyalkyl. In other embodiments, each of R¹, R² and R³ isindependently H, methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl,tert-butyl, isobutyl, sec-butyl, cyclobutyl, pentyl, methoxymethyl,ethoxymethyl, or methoxyethoxymethyl. In certain embodiments, the baseis selected from the group consisting of ammonia, methylamine,ethylamine, propylamine, isopropylamine, cyclopropylamine, butylamine,N-butylamine, tert-butylamine, isobutylamine, sec-butylamine,cyclobutylamine, dimethylamine, N-ethylmethylamine, diethylamine,N-methylpropylamine, N-methylcyclopropanamine, N-ethyl-N-propylamine,N,2-dimethyl-1-propanamine, N-tert-butylmethylamine, diisopropylamine,N-methyl-tert-butylamine, trimethylamine, N,N-dimethylethylamine,N,N-diethylmethylamine, N,N-dimethylisopropylamine, triethylamine andcombinations thereof.

In certain embodiments, the cathode active material is selected from thegroup consisting of Li_(1+x)Ni_(a)Mn_(b)Co_(c)Al_((1−a−b−c))O₂,LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂, LiNi_(0.4)Mn_(0.4)Co_(0.2)O₂,LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂, LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂,LiNi_(0.7)Mn_(0.15)Co_(0.15)O₂, LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂,LiNi_(0.92)Mn_(0.04)Co_(0.04)O₂, LiNi_(0.8)Co_(0.15)Al_(0.05)O₂, LiCoO₂,LiNiO₂, LiMnO₂, LiMn₂O₄, Li₂MnO₃, and combinations thereof, wherein−0.2≤x≤0.2, 0≤a<1, 0≤b<1, 0≤c<1, and a+b+c≤1.

In some embodiments, the cathode active material comprises or is acore-shell composite having a core and shell structure, wherein the coreand the shell each independently comprise a lithium transition metaloxide selected from the group consisting ofLi_(1+x)Ni_(a)Mn_(b)Co_(c)Al_((1−a−b−c))O₂, LiCoO₂, LiNiO₂, LiMnO₂,LiMn₂O₄, Li₂MnO₃, LiCrO₂, Li₄Ti₅O₁₂, LiV₂O₅, LiTiS₂, LiMoS₂, andcombinations thereof, wherein −0.2≤x≤0.2, 0≤a<1, 0≤b<1, 0≤c<1, anda+b+c≤1.

In certain embodiments, lithium loss of the cathode active material isinhibited by a percentage from about 1 percent to about 50 percent.

In some embodiments, the solvent is water or a mixture of water and analcohol. In certain embodiments, the alcohol is selected from the groupconsisting of ethanol, isopropanol, n-propanol, tert-butanol, n-butanol,and combinations thereof. In some embodiments, the alcohol comprisesfrom about 1% to about 30% of the total weight of the cathode slurry.

In certain embodiments, the cathode slurry further comprises aconductive agent that is selected from the group consisting of carbon,carbon black, graphite, expanded graphite, graphene, graphenenanoplatelets, carbon fibers, carbon nano-fibers, graphitized carbonflake, carbon tubes, carbon nanotubes, activated carbon, mesoporouscarbon and combinations thereof.

In some embodiments, the binder material is selected from the groupconsisting of styrene-butadiene rubber, carboxymethyl cellulose,polyvinylidene fluoride, acrylonitrile copolymer, polyacrylic acid,polyacrylonitrile, poly(vinylidene fluoride)-hexafluoropropene, LA132,LA133, LA138, latex, a salt of alginic acid, and combinations thereof.In further embodiments, the salt of alginic acid comprises a cationselected from the group consisting of Na, Li, K, Ca, NH₄, Mg, Al, andcombinations thereof.

In certain embodiments, the boiling point of the base is lower than 100°C. at a pressure of 1 atm. In certain embodiments, the concentration ofthe base in the cathode slurry is from about 0.5% to about 3.5% byweight, based on the total weight of the cathode slurry.

In some embodiments, the pH of the cathode slurry is from about 8 toabout 14. In some embodiments, the solid content of the cathode slurryis from about 45% to about 75% by weight, based on the total weight ofthe cathode slurry.

In certain embodiments, the cathode slurry is free of a dispersing agentselected from the group consisting of a cationic surfactant, an anionicsurfactant, a nonionic surfactant, an amphoteric surfactant, and apolymeric acid.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart of an embodiment illustrating the steps forpreparing a cathode.

FIG. 2 depicts the D50 particle size distribution of the organic andbase-treated slurries respectively.

FIG. 3 is a graph showing the relationship between the concentration oflithium ions in the cathode slurry and time.

FIGS. 4a and 4b depict the appearance of the surface of cathodeelectrode layers after coating with the untreated and base-treatedslurries respectively.

FIG. 5 is a bar graph showing the peeling strengths of electrodesprepared by different methods.

FIG. 6 shows three specific capacity-voltage curves of the firstdischarge cycle of NMC811.

DETAILED DESCRIPTION OF THE INVENTION

Provided herein is a method of preparing a cathode slurry for asecondary battery, comprising a cathode active material, a binder, asolvent and a base having a formula of R¹R²R³N, wherein each of R¹, R²and R³ is independently H, C₁₋₆ alkyl, C₃₋₆ cycloalkyl, C₁₋₆heteroalkyl, C₄₋₆ cycloalkylalkyl, C₂₋₆ alkoxyalkyl, or C₃₋₆alkoxyalkoxyalkyl, where the C₁₋₆ alkyl, C₃₋₆ cycloalkyl, C₁₋₆heteroalkyl, C₄₋₆ cycloalkylalkyl, C₂₋₆ alkoxyalkyl, or C₃₋₆alkoxyalkoxyalkyl is optionally substituted with one or moresubstituents, where each of the substituents is independently alkyl orcycloalkyl.

The term “electrode” refers to a “cathode” or an “anode.”

The term “positive electrode” is used interchangeably with cathode.Likewise, the term “negative electrode” is used interchangeably withanode.

The term “binder material” refers to a chemical or a substance used tohold an electrode material and/or a conductive agent in place and adherethem onto a conductive metal part to form an electrode. In someembodiments, the electrode does not comprise any conductive agent.

The term “conductive agent” refers to a material which is chemicallyinactive and has good electrical conductivity. Therefore, the conductiveagent is often mixed with an electrode active material at the time offorming an electrode to improve electrical conductivity of theelectrode.

The term “homogenizer” refers to an equipment that can be used forhomogenization of materials. The term “homogenization” refers to aprocess of distributing the materials uniformly throughout a fluid. Anyconventional homogenizers can be used for the method disclosed herein.Some non-limiting examples of the homogenizer include stirring mixers,planetary stirring mixers, blenders and ultrasonicators.

The term “planetary mixer” refers to an equipment that can be used tomix or stir different materials for producing a homogeneous mixture,which consists of blades conducting a planetary motion within a vessel.In some embodiments, the planetary mixer comprises at least oneplanetary blade and at least one high-speed dispersion blade. Theplanetary and the high-speed dispersion blades rotate on their own axesand also rotate continuously around the vessel. The rotation speed canbe expressed in unit of rotations per minute (rpm) which refers to thenumber of rotations that a rotating body completes in one minute.

The term “applying” refers to an act of laying or spreading a substanceon a surface.

The term “current collector” refers to any conductive substrate, whichis in contact with an electrode layer and is capable of conducting anelectrical current flowing to electrodes during discharging or charginga secondary battery. Some non-limiting examples of the current collectorinclude a single conductive metal layer or substrate and a singleconductive metal layer or substrate with an overlying conductive coatinglayer, such as a carbon black-based coating layer. The conductive metallayer or substrate may be in the form of a foil or a porous body havinga three-dimensional network structure, and may be a polymeric ormetallic material or a metalized polymer. In some embodiments, thethree-dimensional porous current collector is covered with a conformalcarbon layer.

The term “electrode layer” refers to a layer, which is in contact with acurrent collector, that comprises an electrochemically active material.In some embodiments, the electrode layer is made by applying a coatingon to the current collector. In some embodiments, the electrode layer islocated on the surface of the current collector. In other embodiments,the three-dimensional porous current collector is coated conformallywith an electrode layer.

The term “doctor blading” refers to a process for fabrication of largearea films on rigid or flexible substrates. A coating thickness can becontrolled by an adjustable gap width between a coating blade and acoating surface, which allows the deposition of variable wet layerthicknesses.

The term “slot-die coating” refers to a process for fabrication of largearea films on rigid or flexible substrates. A slurry is applied to thesubstrate by continuously pumping slurry through a nozzle onto thesubstrate, which is mounted on a roller and constantly fed toward thenozzle. The thickness of the coating is controlled by various methods,such as altering the slurry flow rate or the speed of the roller.

The term “room temperature” refers to indoor temperatures from about 18°C. to about 30° C., e.g., 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28,29, or 30° C. In some embodiments, room temperature refers to atemperature of about 20° C.+/−1° C. or +/−2° C. or +/−3° C. In otherembodiments, room temperature refers to a temperature of about 22° C. orabout 25° C.

The term “particle size D50” refers to a volume-based accumulative 50%size (D50), which is a particle size at a point of 50% on anaccumulative curve (i.e., a diameter of a particle in the 50thpercentile (median) of the volumes of particles) when the accumulativecurve is drawn so that a particle size distribution is obtained on thevolume basis and the whole volume is 100%. Further, with respect to thecathode active material of the present invention, the particle size D50means a volume-averaged particle size of secondary particles which canbe formed by mutual agglomeration of primary particles, and in a casewhere the particles are composed of the primary particles only, it meansa volume-averaged particle size of the primary particles.

The term “solid content” refers to the amount of non-volatile materialremaining after evaporation.

The term “peeling strength” refers to the amount of force required toseparate two materials that are bonded to each other, such as a currentcollector and an electrode active material coating. It is a measure ofthe adhesion strength between such two materials and is usuallyexpressed in N/cm.

The term “C rate” refers to the charging or discharging rate of a cellor battery, expressed in terms of its total storage capacity in Ah ormAh. For example, a rate of 1 C means utilization of all of the storedenergy in one hour; a 0.1 C means utilization of 10% of the energy inone hour or full energy in 10 hours; and a 5 C means utilization of fullenergy in 12 minutes.

The term “ampere-hour (Ah)” refers to a unit used in specifying thestorage capacity of a battery. For example, a battery with 1 Ah capacitycan supply a current of one ampere for one hour or 0.5 A for two hours,etc. Therefore, 1 Ampere-hour (Ah) is the equivalent of 3,600 coulombsof electrical charge. Similarly, the term “miniampere-hour (mAh)” alsorefers to a unit of the storage capacity of a battery and is 1/1,000 ofan ampere-hour.

The term “battery cycle life” refers to the number of completecharge/discharge cycles a battery can perform before its nominalcapacity falls below 80% of its initial rated capacity.

The term “capacity” is a characteristic of an electrochemical cell thatrefers to the total amount of electrical charge an electrochemical cell,such as a battery, is able to hold. Capacity is typically expressed inunits of ampere-hours. The term “specific capacity” refers to thecapacity output of an electrochemical cell, such as a battery, per unitweight, usually expressed in Ah/kg or mAh/g.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L), and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R=R^(L)+k*(R^(U)−R^(L)), wherein k is a variable ranging from0 percent to 100 percent. Moreover, any numerical range defined by two Rnumbers as defined in the above is also specifically disclosed.

Generally, lithium-ion battery electrodes are manufactured by casting anorganic-based slurry onto a metallic current collector. The slurrycontains electrode active material, conductive carbon, and binder in anorganic solvent, most commonly N-methyl-2-pyrrolidone (NMP). The binder,most commonly polyvinylidene fluoride (PVDF), is dissolved in thesolvent, and conductive additives as well as the electrode activematerial are suspended in the slurry. PVDF provides a goodelectrochemical stability and high adhesion to the electrode materialsand current collectors. However, PVDF can only dissolve in some specificorganic solvents such as N-methyl-2-pyrrolidone (NMP) which is flammableand toxic and hence requires specific handling.

An NMP recovery system must be in place during the drying process torecover NMP vapors. This will generate significant costs in themanufacturing process since it requires a large capital investment. Theuse of less expensive and more environmentally-friendly solvents, suchas aqueous solvents, is preferred since it can reduce the large capitalcost of the recovery system. The attempts to replace the organicNMP-based coating process with a water-based coating process have beensuccessful for the negative electrode. A typical water-based slurry foranode coating comprises carboxymethyl cellulose (CMC) andstyrene-butadiene rubber (SBR). Within the battery, cathodes are at highvoltage. Most rubbers including SBR are only stable at the low voltageof the anode and will decompose at high voltage. Therefore, contrary toanodes, water-based coating for cathodes is much more difficult.

Another concern of water-based processing is the fact that many cathodeactive materials are not inert in water, which causes problems andcomplicates the implementation of water-based coating process forcathodes. The lithium in cathode active materials may react with H₂O togenerate LiOH, resulting in a degraded electrochemical performance. Ingeneral, the surface of the cathode active material is coated with anion-conductive solid compound in order to enhance its stability towardand compatibility with water-based processing. Acid may also be added tothe solution to adjust the slurry pH by neutralizing the base on thesurface of the cathode active material. However, upon exposure to water,a significant amount of soluble base LiOH will continuously form,damaging the cathode active material at a significant rate.

Accordingly, the present invention provides a method of preparing acathode via the use of a water-based slurry. FIG. 1 is a flow chart ofan embodiment illustrating the steps of method 100 for preparing acathode. The slurry prepared by the method disclosed herein showsimproved stability by minimizing the reactivity of the cathode activematerial with water, thereby enhancing battery performance.

In some embodiments, the first suspension is formed by dispersing acathode active material with an aqueous solution at step 101. In someembodiments, a cathode active material is dispersed in an aqueoussolution to form a first suspension.

Conventional prior art processes for making cathode slurries may requirea step to thoroughly dry the cathode active material or remove thechemical after pre-treatment. One advantage of this invention is thatthe cathode active material is combined with the base and othercomponents such as binders to form a slurry as is, without drying orremoving the base. This leads to faster, more efficient production.

Surprisingly, not all types of basic treatment before forming thecathode active material achieve the same desired effect of the presentinvention. The base should be added after completion of the formation ofthe cathode active material. In some embodiments, the base has a formulaR¹R²R³N, wherein each of R¹, R² and R³ is independently H, C₁₋₆ alkyl,C₃₋₆ cycloalkyl, C₁₋₆ heteroalkyl, C₄₋₆ cycloalkylalkyl, C₂₋₆alkoxyalkyl, or C₃₋₆ alkoxyalkoxyalkyl where the C₁₋₆ alkyl, C₃₋₆cycloalkyl, C₁₋₆ heteroalkyl, C₄₋₆ cycloalkylalkyl, C₂₋₆ alkoxyalkyl, orC₃₋₆ alkoxyalkoxyalkyl is optionally substituted with one or moresubstituents, where each of the substituents is independently alkyl orcycloalkyl.

In some embodiments, the base has a formula R¹R²R³N, wherein each of R¹,R² and R³ is independently C₁₋₄ alkyl, C₃₋₅ cycloalkyl, C₁₋₄heteroalkyl, C₂₋₄ alkoxyalkyl, or C₃₋₅ alkoxyalkoxyalkyl. In certainembodiments, the base is selected from a compound having formulaR¹R²R³N, wherein each of R¹, R² and R³ is independently H, methyl,ethyl, propyl, isopropyl, cyclopropyl, n-butyl, tert-butyl, isobutyl,sec-butyl, cyclobutyl, pentyl, methoxymethyl, ethoxymethyl, ormethoxyethoxymethyl.

In some embodiments, the base is ammonia, a primary amine, secondaryamine, tertiary amine or a combination thereof. In some embodiments, thebase is a primary amine selected from the group consisting ofmethylamine, ethylamine, propylamine, isopropylamine, cyclopropylamine,butylamine, N-butylamine, tert-butylamine, isobutylamine,sec-butylamine, cyclobutylamine and combinations thereof. In certainembodiments, the base is a secondary amine selected from the groupconsisting of dimethylamine, N-ethylmethylamine, diethylamine,N-methylpropylamine, N-methylcyclopropanamine, N-ethyl-N-propylamine,N,2-dimethyl-1-propanamine, N-tert-butylmethylamine, diisopropylamineand combinations thereof. In some embodiments, the base is a tertiaryamine selected from the group consisting of trimethylamine,N,N-dimethylethylamine, N,N-diethylmethylamine,N,N-dimethylisopropylamine, triethylamine and combinations thereof.

In some embodiments, the pH of the first suspension is from about 8 toabout 14, from about 8 to about 13.5, from about 8 to about 13, fromabout 8 to about 12.5, from about 8 to about 12, from about 8 to about11.5, from about 8 to about 11, from about 8 to about 10.5, from about 8to about 10, from about 8 to about 9, from about 8.5 to about 14, fromabout 8.5 to about 13, from about 8.5 to about 12, from about 8.5 toabout 11, from about 8.5 to about 10.5, from about 9 to about 14, fromabout 9 to about 13, from about 9 to about 12, from about 9 to about 11,from about 9 to about 10, from about 10 to about 14, from about 10 toabout 13, from about 10 to about 12, from about 10 to about 11, fromabout 11 to about 14, from about 11 to about 13, from about 11 to about12, from about 12 to about 14, or from about 12 to about 13. In certainembodiments, the pH of the first suspension is less than 14, less than13.5, less than 13, less than 12.5, less than 12, less than 11.5, lessthan 11, less than 10.5, less than 10, less than 9.5, less than 9, orless than 8.5. In some embodiments, the pH of the first suspension isgreater than 8, greater than 8.5, greater than 9, greater than 9.5,greater than 10, greater than 10.5, greater than 11, greater than 11.5,greater than 12, greater than 12.5, greater than 13, or greater than13.5.

The cathode active material is dispersed in the aqueous solution to forma first suspension, so that the cathode active material is treated withthe base in the aqueous solution. When exposed to the base, thestability of the cathode active material in water is enhanced. It isdesired and necessary to allow the cathode active material to be treatedin the first suspension for some time before the addition of otherelectrode components such as binders and conductive agents. The cathodeactive material should be treated in the aqueous solution for less thanabout 1 hour. If the treating time is shorter than 1 minute, the cathodeactive material does not receive sufficient treatment, while treatingtimes above 60 minutes may result in degradation of the cathode activematerial. In some embodiments, the cathode active material is treatedwith the aqueous solution for a time period from about 1 minute to about60 minutes, from about 1 minute to about 50 minutes, from about 1 minuteto about 40 minutes, from about 1 minute to about 30 minutes, from about1 minute to about 20 minutes, from about 1 minute to about 10 minutes,from about 5 minutes to about 60 minutes, from about 5 minutes to about50 minutes, from about 5 minutes to about 40 minutes, from about 5minutes to about 30 minutes, from about 5 minutes to about 20 minutes,from about 5 minutes to about 10 minutes, from about 10 minutes to about60 minutes, from about 10 minutes to about 50 minutes, from about 10minutes to about 40 minutes, from about 10 minutes to about 30 minutes,from about 10 minutes to about 20 minutes, from about 15 minutes toabout 60 minutes, from about 15 minutes to about 50 minutes, from about15 minutes to about 40 minutes, from about 15 minutes to about 30minutes, from about 15 minutes to about 20 minutes, from about 20minutes to about 50 minutes, from about 20 minutes to about 40 minutes,or from about 20 minutes to about 30 minutes.

In certain embodiments, the cathode active material is treated with theaqueous solution for a time period less than 60 minutes, less than 55minutes, less than 50 minutes, less than 45 minutes, less than 40minutes, less than 35 minutes, less than 30 minutes, less than 25minutes, less than 20 minutes, less than 15 minutes, less than 10minutes, or less than 5 minutes. In some embodiments, the cathode activematerial is treated with the aqueous solution for a time period of morethan about 55 minutes, more than about 50 minutes, more than about 45minutes, more than about 40 minutes, more than about 35 minutes, morethan about 30 minutes, more than about 25 minutes, more than about 20minutes, more than about 15 minutes, more than about 10 minutes, or morethan about 5 minutes.

After dispersing the cathode active material in the aqueous solution,the mixture may be stirred or left to rest to form the first suspension.In some embodiments, the mixture may be stirred or left to rest for atime period from about 10 minutes to 60 minutes, from about 15 minutesto about 60 minutes, from about 20 minutes to about 60 minutes, fromabout 30 minutes to about 60 minutes, from about 10 minutes to about 45minutes, from about 10 minutes to about 30 minutes, or from about 20minutes to about 45 minutes.

It is found that the treatment of the cathode active material with theaqueous solution should be performed at a temperature range from about5° C. to about 35° C. in order to avoid undesired effects on batteryperformance, such as reduced capacity and cyclability performance. Insome embodiments, the cathode active material is treated with theaqueous solution at a temperature range from about 5° C. to about 30°C., from about 5° C. to about 25° C., from about 5° C. to about 20° C.,from about 5° C. to about 15° C., or from about 5° C. to about 10° C. Incertain embodiments, the cathode active material is treated with theaqueous solution at a temperature of less than 30° C., less than 25° C.,less than 20° C., less than 15° C., or less than 10° C. In someembodiments, the cathode active material is treated with the aqueoussolution at a temperature of higher than about 25° C., higher than about20° C., higher than about 15° C., higher than about 10° C., or higherthan about 5° C.

The concentration of the base in the first suspension critically impactsthe battery performance. In some embodiments, the concentration of thebase in the aqueous solution is from about 1% to about 30% by weight,based on the total weight of the aqueous solution. In certainembodiments, the concentration of the base in the aqueous solution isfrom about 1% to about 25%, from about 1% to about 20%, from about 1% toabout 15%, from about 1% to about 10%, from about 1% to about 5%, fromabout 4% to about 10%, from about 4% to about 8%, from about 5% to about25%, from about 5% to about 20%, from about 5% to about 15%, from about7% to about 15%, from about 7% to about 13%, from about 10% to about25%, from about 10% to about 20%, from about 10% to about 15%, fromabout 15% to about 25%, or from about 15% to about 20% by weight, basedon the total weight of the aqueous solution. In some embodiments, theamount of base in the aqueous solution is less than 30%, less than 25%,less than 20%, less than 15%, less than 10%, less than 5%, or less than1% by weight, based on the total weight of the aqueous solution. In someembodiments, a low concentration of the base in the first suspension isinsufficient to cause any noticeable changes in the battery performance.The concentration of the base in the aqueous solution should be higherthan about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about13%, about 15% or about 20% by weight, based on the total weight of theaqueous solution.

In some embodiments, the boiling point of the base is lower than orequal to the boiling point of water. When the coated film is oven dried,the base is often removed before the slurry solvent is substantiallyremoved. In some embodiments, the boiling point of the base is lowerthan 100° C., lower than 90° C., lower than 80° C., lower than 70° C.,lower than 60° C., lower than 50° C., lower than 40° C., lower than 30°C., lower than 20° C., lower than 10° C., or lower than 0° C., at apressure of 1 atmosphere (atm). In certain embodiments, the boilingpoint of the base is higher than −40° C., higher than −30° C., higherthan −20° C., higher than −10° C., higher than 10° C., higher than 20°C., higher than 30° C., higher than 40° C., higher than 50° C., higherthan 60° C., higher than 70° C., higher than 80° C., or higher than 90°C., at a pressure of 1 atm. In some embodiments, the base has a boilingpoint between −40° C. and 100° C., between −40° C. and 80° C., between−40° C. and 60° C., between −40° C. and 50° C., between −40° C. and 40°C., between 10° C. and 90° C., between 10° C. and 80° C., between 20° C.and 80° C., between 20° C. and 50° C., or between −40° C. and 30° C., ata pressure of 1 atm.

In some embodiments, the active battery electrode material is a cathodeactive material, wherein the cathode active material is selected fromthe group consisting of LiCoO₂, LiNiO₂, LiNi_(x)Mn_(y)O₂,Li_(1+z)Ni_(x)Mn_(y)Co_(1−x−y)O₂, LiNi_(x)Co_(y)Al_(z)O₂, LiV₂O₅,LiTiS₂, LiMoS₂, LiMnO₂, LiCrO₂, LiMn₂O₄, LiFeO₂, LiFePO₄, andcombinations thereof, wherein each x is independently from 0.3 to 0.8;each y is independently from 0.1 to 0.45; and each z is independentlyfrom 0 to 0.2. In certain embodiments, the cathode active material isselected from the group consisting of LiCoO₂, LiNiO₂, LiNi_(x)Mn_(y)O₂,Li_(1+z)Ni_(x)Mn_(y)Co_(1−x−y)O₂ (NMC), LiNi_(x)Co_(y)Al_(z)O₂, LiV₂O₅,LiTiS₂, LiMoS₂, LiMnO₂, LiCrO₂, LiMn₂O₄, LiFeO₂, LiFePO₄, andcombinations thereof, wherein each x is independently from 0.4 to 0.6;each y is independently from 0.2 to 0.4; and each z is independentlyfrom 0 to 0.1. In other embodiments, the cathode active material is notLiCoO₂, LiNiO₂, LiV₂O₅, LiTiS₂, LiMoS₂, LiMnO₂, LiCrO₂, LiMn₂O₄, LiFeO₂,or LiFePO₄. In further embodiments, the cathode active material is notLiNi_(x)Mn_(y)O₂, Li_(1+z)Ni_(x)Mn_(y)Co_(1−x−y)O₂, orLiNi_(x)Co_(y)Al_(z)O₂, wherein each x is independently from 0.3 to 0.8;each y is independently from 0.1 to 0.45; and each z is independentlyfrom 0 to 0.2.

In certain embodiments, the cathode active material is doped with adopant selected from the group consisting of Fe, Ni, Mn, Al, Mg, Zn, Ti,La, Ce, Sn, Zr, Ru, Si, Ge, and combinations thereof. In someembodiments, the dopant is not Fe, Ni, Mn, Mg, Zn, Ti, La, Ce, Ru, Si,or Ge. In certain embodiments, the dopant is not Al, Sn, or Zr.

The method disclosed herein is particularly suitable for preparing acathode using a nickel-containing cathode active material.Nickel-containing cathodes prepared by the method disclosed herein haveimproved electrochemical performance and long-term stability.

In some embodiments, the cathode active material isLi_(1+x)Ni_(a)Mn_(b)Co_(c)Al_((1−a−b−c))O₂,LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂(NMC333), LiNiO₄MnO₄Co_(0.2)O₂,LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂ (NMC532), LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂(NMC622), LiNi_(0.7)Mn_(0.15)Co_(0.15)O₂, LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂(NMC811), LiNi_(0.92)Mn_(0.04)Co_(0.04)O₂,LiNi_(0.8)Co_(0.15)Al_(0.005)O₂ (NCA), LiCoO₂ (LCO), LiNiO₂ (LNO),LiMnO₂, LiMn₂O₄(LMO), Li₂MnO₃, and combinations thereof, wherein−0.2≤x≤0.2, 0≤a<1, 0≤b<1, 0≤c<1, and a+b+c≤1. In certain embodiments,the cathode active material isLi_(1+x)Ni_(a)Mn_(b)Co_(c)Al_((1−a−b−c))O₂; wherein −0.2≤x≤0.2, 0≤a<1,0≤b<1, 0≤c<1, and a+b+c<1. In some embodiments, the cathode activematerial has the general formulaLi_(1+x)Ni_(a)Mn_(b)Co_(c)Al_((1−a−b−c))O₂, with 0.33≤a≤0.92,0.33≤a≤0.9, 0.33≤a≤0.8, 0.5≤a≤0.92, 0.5≤a≤0.9, 0.5≤a≤0.8, 0.6≤a≤0.92, or0.6≤a≤0.9; 0≤b≤0.5, 0≤b≤0.3, 0.1≤b≤0.5, 0.1≤b≤0.4, 0.1≤b≤0.3, 0.1≤b≤0.2,or 0.2≤b≤0.5; 0≤c≤0.5, 0≤c≤0.3, 0.1≤c≤0.5, 0.1≤c≤0.4, 0.1≤c≤0.3,0.1≤c≤0.2, or 0.2≤c≤0.5.

In other embodiments, the cathode active material is not LiCoO₂, LiNiO₂,LiMnO₂, LiMn₂O₄, or Li₂MnO₃. In further embodiments, the cathode activematerial is not LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂,LiNi_(0.4)Mn_(0.4)Co_(0.2)O₂, LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂,LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂, LiNi_(0.7)Mn_(0.15)Co_(0.15)O₂,LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂, LiNi_(0.92)Mn_(0.04)Co_(0.04)O₂, orLiNi_(0.8)Co_(0.15)Al_(0.05)O₂.

In certain embodiments, the cathode active material comprises or is acore-shell composite having a core and shell structure, wherein the coreand the shell each independently comprise a lithium transition metaloxide selected from the group consisting ofLi_(1+x)Ni_(a)Mn_(b)Co_(c)Al_((1−a−b−c))O₂, LiCoO₂, LiNiO₂, LiMnO₂,LiMn₂O₄, Li₂MnO₃, LiCrO₂, Li₄Ti₅O₁₂, LiV₂O₅, LiTiS₂, LiMoS₂, andcombinations thereof, wherein −0.2≤x≤0.2, 0≤a<1, 0≤b<1, 0≤c<1, anda+b+c<1. In other embodiments, the core and the shell each independentlycomprise two or more lithium transition metal oxides. In someembodiments, one of the core or shell comprises only one lithiumtransition metal oxide, while the other comprises two or more lithiumtransition metal oxides. The lithium transition metal oxide or oxides inthe core and the shell may be the same, or they may be different orpartially different. In some embodiments, the two or more lithiumtransition metal oxides are uniformly distributed over the core. Incertain embodiments, the two or more lithium transition metal oxides arenot uniformly distributed over the core. In some embodiments, thecathode active material is not a core-shell composite.

In some embodiments, each of the lithium transition metal oxides in thecore and the shell is independently doped with a dopant selected fromthe group consisting of Fe, Ni, Mn, Al, Mg, Zn, Ti, La, Ce, Sn, Zr, Ru,Si, Ge, and combinations thereof. In certain embodiments, the core andthe shell each independently comprise two or more doped lithiumtransition metal oxides. In some embodiments, the two or more dopedlithium transition metal oxides are uniformly distributed over the core.In certain embodiments, the two or more doped lithium transition metaloxides are not uniformly distributed over the core.

In some embodiments, the diameter of the core is from about 5 μm toabout 45 μm, from about 5 μm to about 35 μm, from about 5 μm to about 25μm, from about 10 μm to about 40 μm, or from about 10 μm to about 35 μm.In certain embodiments, the thickness of the shell is from about 1 μm toabout 45 μm, from about 1 μm to about 35 μm, from about 1 μm to about 25μm, from about 1 μm to about 15 μm, from about 1 μm to about 10 μm, fromabout 1 μm to about 5 μm, from about 3 μm to about 15 μm, from about 3μm to about 10 μm, from about 5 μm to about 10 μm, from about 10 μm toabout 45 μm, from about 10 μm to about 35 μm, from about 10 μm to about25 μm, from about 15 μm to about 45 μm, from about 15 μm to about 30 μm,from about 15 μm to about 25 μm, from about 20 μm to about 35 μm, orfrom about 20 μm to about 30 μm. In certain embodiments, the diameter orthickness ratio of the core and the shell are in the range of 15:85 to85:15, 25:75 to 75:25, 30:70 to 70:30, or 40:60 to 60:40. In certainembodiments, the volume or weight ratio of the core and the shell is95:5, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, or 30:70.

In some embodiments, the second suspension is formed by dispersing abinder material and a conductive agent in water at step 102.

Any suitable material can be used as the binder material. Somenon-limiting examples include styrene-butadiene rubber (SBR),carboxymethyl cellulose (CMC), acrylonitrile copolymer, polyacrylic acid(PAA), polyacrylonitrile (PAN), LA132, LA133, LA138, latex, a salt ofalginic acid, polyvinylidene fluoride (PVDF), poly(vinylidenefluoride)-hexafluoropropene (PVDF-HFP), polytetrafluoroethylene (PTFE),polystyrene, poly(vinyl alcohol) (PVA), poly(vinyl acetate),polyisoprene, polyaniline, polyethylene, polyimide, polyurethane,polyvinyl butyral, polyvinyl pyrrolidone (PVP), gelatin, chitosan,starch, agar-agar, xanthan gum, gum arabic, gellan gum, guar gum, gumkaraya, tara gum, gum tragacanth, casein, amylose, pectin, carrageenans,and combinations thereof. In further embodiments, the salt of alginicacid comprises a cation selected from Na, Li, K, Ca, NH₄, Mg, Al, or acombination thereof. In certain embodiments, the binder material is freeof styrene-butadiene rubber, carboxymethyl cellulose, acrylonitrilecopolymer, polyacrylic acid, polyacrylonitrile, LA132, LA133, LA138,latex, a salt of alginic acid, polyvinylidene fluoride, poly(vinylidenefluoride)-hexafluoropropene, polytetrafluoroethylene, polystyrene,poly(vinyl alcohol), poly(vinyl acetate), polyisoprene, polyaniline,polyethylene, polyimide, polyurethane, polyvinyl butyral, polyvinylpyrrolidone, gelatin, chitosan, starch, agar-agar, xanthan gum, gumarabic, gellan gum, guar gum, gum karaya, tara gum, gum tragacanth,casein, amylose, pectin or carrageenans. In certain embodiments, thebinder material is not a fluorine-containing polymer such as PVDF,PVDF-HFP or PTFE.

Any suitable material can be used as the conductive agent. In someembodiments, the conductive agent is a carbonaceous material. Somenon-limiting examples include carbon, carbon black, graphite, expandedgraphite, graphene, graphene nanoplatelets, carbon fibers, carbonnano-fibers, graphitized carbon flake, carbon tubes, carbon nanotubes,activated carbon, mesoporous carbon, and combinations thereof. Incertain embodiments, the conductive agent does not comprise acarbonaceous material.

In some embodiments, the conductive agent is a conductive polymerselected from the group consisting of polypyrrole, polyaniline,polyacetylene, polyphenylene sulfide (PPS), polyphenylene vinylene(PPV), poly(3,4-ethylenedioxythiophene) (PEDOT), polythiophene andcombinations thereof. In some embodiments, the conductive agent playstwo roles simultaneously not only as a conductive agent but also as abinder. In certain embodiments, the positive electrode layer comprisestwo components, the cathode active material and conductive polymer. Inother embodiments, the positive electrode layer comprises the cathodeactive material, conductive agent and conductive polymer. In certainembodiments, the conductive polymer is an additive and the positiveelectrode layer comprises the cathode active material, conductive agent,binder and conductive polymer. In other embodiments, the positiveelectrode layer does not comprise a conductive polymer.

In certain embodiments, the amount of each of the binder material andthe conductive material in the second suspension is independently fromabout 1% to about 20%, from about 1% to about 15%, from about 1% toabout 10%, from about 1% to about 5%, from about 3% to about 20%, fromabout 5% to about 20%, from about 5% to about 10%, from about 10% toabout 20%, from about 10% to about 15%, or from about 15% to about 20%by weight, based on the total weight of the second suspension. In someembodiments, the amount of each of the binder material and theconductive material in the second suspension is independently less than20%, less than 15%, less than 10%, less than 8%, or less than 6% byweight, based on the total weight of the second suspension.

In some embodiments, the solid content of the second suspension is fromabout 10% to about 25%, from about 10% to about 20%, from about 10% toabout 18%, from about 12% to about 25%, from about 12% to about 20%,from about 12% to about 18%, from about 15% to about 25%, from about 15%to about 20%, or from about 18% to 25% by weight, based on the totalweight of the second suspension. In certain embodiments, the solidcontent of the second suspension is about 10%, about 12%, about 15%,about 18%, about 20%, or about 25% by weight, based on the total weightof the second suspension. In certain embodiments, the solid content ofthe second suspension is at least 10%, at least 12%, at least 15%, atleast 18%, or at least 20% by weight, based on the total weight of thesecond suspension. In certain embodiments, the solid content of thesecond suspension is less than less than 25%, less than 20%, less than18%, or less than 15% by weight, based on the total weight of the secondsuspension.

In some embodiments, the second suspension is mixed at a temperaturefrom about 10° C. to about 40° C., from about 10° C. to about 35° C.,from about 10° C. to about 30° C., from about 10° C. to about 25° C.,from about 10° C. to about 20° C., or from about 10° C. to about 15° C.In some embodiments, the second suspension is mixed at a temperature ofless than 40° C., less than 35° C., less than 30° C., less than 25° C.,less than 20° C., less than 15° C., or less than 10° C. In someembodiments, the second suspension is mixed at a temperature of about40° C., about 35° C., about 30° C., about 25° C., about 20° C., about15° C., or about 10° C.

Mixing the binder material and conductive agent in the second suspensioncan be done while the cathode active material is being treated in thefirst suspension. This is advantageous as it allows quicker processingand better dispersion of materials in the third suspension. However,this is by no means required. In certain embodiments, the bindermaterial and conductive agent are not mixed separately as a secondsuspension, but directly added in the first suspension and thenhomogenized by a homogenizer to obtain a homogenized cathode slurry. Insome embodiments, the binder material and conductive agent aresimultaneously or sequentially added to the first suspension alreadycontaining the cathode active material after treating the cathode activematerial, wherein the concentration of the base in the first suspensioncan be adjusted to the desired concentration of the base in the thirdsuspension before or after adding the binder material and conductiveagent. When adding the binder material and conductive agent sequentiallywithout forming the second suspension, stirring or dispersion may beemployed between the additions.

In some embodiments, the third suspension is formed by mixing the firstsuspension with the second suspension at step 103.

In some embodiments, the concentration of the base in the thirdsuspension is from about 0.25% to about 3.5%, from about 0.25% to about3.0%, from about 0.25% to about 2.5%, from about 0.25% to about 2.0%,from about 0.25% to about 1.75%, from about 0.25% to about 1.6%, fromabout 0.25% to about 1.5%, from about 0.25% to about 1.25%, from about0.25% to about 1%, from about 0.3% to about 1.75%, from about 0.3% toabout 1.6%, from about 0.3% to about 1.5%, from about 0.3% to about1.25%, from about 0.3% to about 1%, from about 0.5% to about 2.5%, fromabout 0.5% to about 2.0%, from about 0.5% to about 1.75%, from about0.5% to about 1.6%, from about 0.5% to about 1.5%, from about 0.5% toabout 1.25%, from about 0.75% to about 2.5%, from about 0.75% to about2.0%, from about 0.75% to about 1.75%, from about 0.75% to about 1.6%,or from about 0.75% to about 1.5% by weight, based on the total weightof the third suspension. In some embodiments, the concentration of thebase in the third suspension is more than 0.25%, more than 0.3%, morethan 0.5%, more than 0.75%, more than 1.0%, more than 1.25%, more than1.5%, more than 1.6%, more than 1.8%, more than 2.0%, or more than 2.5%by weight, based on the total weight of the third suspension. In someembodiments, the concentration of the base in the third suspension isless than 3.5%, less than 3.0%, less than 2.5%, less than 2.0%, lessthan 1.75%, less than 1.6%, less than 1.5%, less than 1.25%, less than1%, less than 0.75%, or less than 0.5% by weight, based on the totalweight of the third suspension. In some embodiments, the concentrationof the base in the third suspension is about 0.25%, about 0.3%, about0.5%, about 0.75%, about 1.0%, about 1.25%, about 1.5%, about 1.6%,about 2.0%, about 2.5%, about 3.0%, or about 3.5% by weight, based onthe total weight of the third suspension. The concentration of the basein the third suspension is equal to the concentration of the base in thehomogenized cathode slurry.

In some embodiments, before homogenization of the third suspension, thethird suspension is degassed under a reduced pressure for a short periodof time to remove air bubbles trapped in the suspension. In someembodiments, the third suspension is degassed at a pressure from about 1kPa to about 20 kPa, from about 1 kPa to about 15 kPa, from about 1 kPato about 10 kPa, from about 5 kPa to about 20 kPa, from about 5 kPa toabout 15 kPa, or from about 10 kPa to about 20 kPa. In certainembodiments, the suspension is degassed at a pressure less than 20 kPa,less than 15 kPa, or less than 10 kPa. In some embodiments, thesuspension is degassed for a time period from about 30 minutes to about4 hours, from about 1 hour to about 4 hours, from about 2 hours to about4 hours, or from about 30 minutes to about 2 hours. In certainembodiments, the third suspension is degassed for a time period lessthan 4 hours, less than 2 hours, or less than 1 hour.

In certain embodiments, the third suspension is degassed afterhomogenization. The homogenized third suspension may also be degassed atthe pressures and for the time durations stated in the step of degassingthe third suspension before homogenization.

At step 103, the third suspension is homogenized by a homogenizer at atemperature from about 10° C. to about 30° C. to obtain a cathodeslurry. The homogenizer may be equipped with a temperature controlsystem and the temperature of the third suspension can be controlled bythe temperature control system. Any homogenizer that can reduce oreliminate particle aggregation, and/or promote homogeneous distributionof slurry ingredients can be used herein. Homogeneous distribution playsan important role in fabricating batteries with good batteryperformance. In some embodiments, the homogenizer is a planetarystirring mixer, a stirring mixer, a blender, or an ultrasonicator.

In some embodiments, the third suspension is homogenized at atemperature from about 10° C. to about 30° C., from about 10° C. toabout 25° C., from about 10° C. to about 20° C., or from about 10° C. toabout 15° C. In some embodiments, the third suspension is homogenized ata temperature of less than 30° C., less than 25° C., less than 20° C.,or less than 15° C.

In some embodiments, the planetary stirring mixer comprises at least oneplanetary blade and at least one high-speed dispersion blade. In certainembodiments, the rotational speed of the planetary blade is from about20 rpm to about 200 rpm, from about 20 rpm to about 150 rpm, from about30 rpm to about 150 rpm, or from about 50 rpm to about 100 rpm. Incertain embodiments, the rotational speed of the dispersion blade isfrom about 1,000 rpm to about 4,000 rpm, from about 1,000 rpm to about3,500 rpm, from about 1,000 rpm to about 3,000 rpm, from about 1,000 rpmto about 2,000 rpm, from about 1,500 rpm to about 3,000 rpm, or fromabout 1,500 rpm to about 2,500 rpm.

When the cathode active material is homogenized in an aqueous slurry fora long period of time, water can damage the cathode active material evenunder the presence of the base in the third suspension. In someembodiments, the third suspension is homogenized for a time period fromabout 10 minutes to about 6 hours, from about 10 minutes to about 5hours, from about 10 minutes to about 4 hours, from about 10 minutes toabout 3 hours, from about 10 minutes to about 2 hours, from about 10minutes to about 1 hour, from about 10 minutes to about 30 minutes, fromabout 30 minutes to about 3 hours, from about 30 minutes to about 2hours, from about 30 minutes to about 1 hour, from about 1 hour to about6 hours, from about 1 hour to about 5 hours, from about 1 hour to about4 hours, from about 1 hour to about 3 hours, from about 1 hour to about2 hours, from about 2 hours to about 6 hours, from about 2 hours toabout 4 hours, from about 2 hours to about 3 hours, from about 3 hoursto about 5 hours, or from about 4 hours to about 6 hours. In certainembodiments, the third suspension is homogenized for a time period lessthan 6 hours, less than 5 hours, less than 4 hours, less than 3 hours,less than 2 hours, less than 1 hour, or less than 30 minutes. In someembodiments, the third suspension is homogenized for a time period ofmore than about 6 hours, more than about 5 hours, more than about 4hours, more than about 3 hours, more than about 2 hours, more than about1 hour, more than about 30 minutes, more than about 20 minutes, or morethan about 10 minutes.

The most common method for achieving homogeneity is to use a highstirring rate, ideally inducing a turbulent flow. However, an increasein stirring rate usually leads to a huge increase in energy demand andthe stresses required to achieve turbulent flow often exceed equipmentcapabilities. Moreover, such stresses can damage the cathode activematerial because some cathode active materials are shear-sensitive. Anadvantage of this invention is that the addition of the base stabilizesthe pH of the slurry, which in turn stabilizes the viscosity of theslurry. This makes it easier to homogenize the slurry and results inefficient mixing under gentle stirring conditions. Another advantage ofthis invention is the reduction in the time required for the admixedcomponents to reach homogeneity.

When the pH value of the slurry varies during homogenization and isoutside of certain ranges, it may affect dispersion homogeneity andparticle size distribution of the water-insoluble components, e.g.,electrode active material and conductive agent in the slurry, therebyresulting in poor electrode performance. Accordingly, it is desirable tomaintain a constant pH in the slurry during homogenization.

In some embodiments, the pH of the homogenized cathode slurry is fromabout 8 to about 14, from about 8 to about 13.5, from about 8 to about13, from about 8 to about 12.5, from about 8 to about 12, from about 8to about 11.5, from about 8 to about 11, from about 8 to about 10.5,from about 8 to about 10, from about 8 to about 9, from about 9 to about14, from about 9 to about 13, from about 9 to about 12, from about 9 toabout 11, from about 10 to about 14, from about 10 to about 13, fromabout 10 to about 12, from about 10 to about 11, from about 10.5 toabout 14, from about 10.5 to about 13.5, from about 10.5 to about 13,from about 10.5 to about 12.5, from about 10.5 to about 12, from about10.5 to about 11.5, from about 11 to about 14, from about 11 to about13, from about 11 to about 12, from about 11.5 to about 12.5, from about11.5 to about 12, or from about 12 to about 14. In certain embodiments,the pH of the homogenized cathode slurry is less than 14, less than13.5, less than 13, less than 12.5, less than 12, less than 11.5, lessthan 11, less than 10.5, less than 10, less than 9.5, less than 9, lessthan 8.5, or less than 8. In some embodiments, the pH of the homogenizedcathode slurry is about 7, about 7.5, about 8, about 8.5, about 9, about9.5, about 10, about 10.5, about 11, about 11.5, about 12, about 12.5,about 13, about 13.5 or about 14.

In certain embodiments, the amount of the conductive agent in thehomogenized cathode slurry is from about 0.5% to about 5%, from about0.5% to about 3%, from about 1% to about 5%, from about 1% to about 4%,or from about 2% to about 3% by weight, based on the total weight of thehomogenized cathode slurry.

In some embodiments, the amount of the conductive agent in thehomogenized cathode slurry is at least about 0.5%, at least about 1%, atleast about 2%, at least about 3%, or at least about 4% by weight, basedon the total weight of the homogenized cathode slurry. In certainembodiments, the amount of the conductive agent in the homogenizedcathode slurry is at most about 1%, at most about 2%, at most about 3%,at most about 4%, or at most about 5% by weight, based on the totalweight of the homogenized cathode slurry.

In certain embodiments, the amount of the binder material in thehomogenized cathode slurry is from about 1% to about 15%, from about 1%to about 10%, from about 1% to about 5%, from about 3% to about 15%,from about 5% to about 15%, from about 5% to about 10%, or from about10% to about 15% by weight, based on the total weight of the homogenizedcathode slurry. In some embodiments, the amount of the binder materialin the homogenized cathode slurry is less than 15%, less than 10%, lessthan 8%, or less than 6% by weight, based on the total weight of thehomogenized cathode slurry.

In some embodiments, the weight of the binder material is greater than,smaller than, or equal to the weight of the conductive agent in thehomogenized cathode slurry. In certain embodiments, the ratio of theweight of the binder material to the weight of the conductive agent isfrom about 1:10 to about 10:1, from about 1:10 to about 5:1, from about1:10 to about 1:1, from about 1:10 to about 1:5, from about 1:5 to about5:1, from about 1:3 to about 3:1, from about 1:2 to about 2:1, or fromabout 1:1.5 to about 1.5:1.

In some embodiments, the solid content of the homogenized cathode slurryis from about 40% to about 80%, from about 45% to about 75%, from about45% to about 70%, from about 45% to about 65%, from about 45% to about60%, from about 45% to about 55%, from about 45% to about 50%, fromabout 50% to about 75%, from about 50% to about 70%, from about 50% toabout 65%, from about 55% to about 75%, from about 55% to about 70%,from about 60% to about 75%, or from about 65% to about 75% by weight,based on the total weight of the homogenized cathode slurry. In certainembodiments, the solid content of the homogenized cathode slurry isabout 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about70%, about 75%, or about 80% by weight, based on the total weight of thehomogenized cathode slurry. In certain embodiments, the solid content ofthe homogenized cathode slurry is at least 40%, at least 45%, at least50%, at least 55%, at least 60%, at least 65%, or at least 70% byweight, based on the total weight of the homogenized cathode slurry. Incertain embodiments, the solid content of the homogenized cathode slurryis less than 75%, less than 70%, less than 65%, less than 60%, less than55%, or less than 50% by weight, based on the total weight of thehomogenized cathode slurry.

The homogenized cathode slurry of the present invention can have ahigher solid content than conventional cathode active material slurries.This allows more cathode active material to be prepared for furtherprocessing at any one time, thus improving efficiency and maximizingproductivity.

High viscosity of the slurry makes it difficult to disperse the bulkmaterials to obtain a uniform slurry. The solvent used in thehomogenized cathode slurry disclosed herein can comprise at least onealcohol. The addition of the alcohol can improve the processability ofthe slurry and lower the freezing point of water. Some non-limitingexamples of suitable alcohol include ethanol, isopropanol, n-propanol,tert-butanol, n-butanol, and combinations thereof. The total amount ofthe alcohol can range from about 1% to about 30%, from about 1% to about20%, from about 1% to about 10%, from about 1% to about 5%, from about1% to about 3%, from about 3% to about 30%, from about 3% to about 20%,from about 3% to about 10%, from about 5% to about 20%, from about 5% toabout 15%, from about 5% to about 10%, or from about 8% to about 15% byweight, based on the total weight of the homogenized cathode slurry. Insome embodiments, the slurry does not comprise an alcohol.

The viscosity of the homogenized cathode slurry is preferably less thanabout 8,000 mPa·s. In some embodiments, the viscosity of the homogenizedcathode slurry is from about 1,000 mPa·s to about 8,000 mPa·s, fromabout 1,000 mPa·s to about 7,000 mPa·s, from about 1,000 mPa·s to about6,000 mPa·s, from about 1,000 mPa·s to about 5,000 mPa·s, from about1,000 mPa·s to about 4,000 mPa·s, from about 1,000 mPa·s to about 3,000mPa·s, from about 1,000 mPa·s to about 2,500 mPa·s, or from about 1,000mPa·s to about 2,000 mPa s. In certain embodiments, the viscosity of thehomogenized cathode slurry is less than 8,000 mPa·s, less than 7,000mPa·s, less than 6,000 mPa·s, less than 5,000 mPa·s, less than 4,000mPa·s, less than 3,000 mPa·s, less than 2,500 mPa·s, less than 2,000mPa·s, less than 1,500 mPa·s, or less than 1,000 mPa·s. In someembodiments, the viscosity of the homogenized cathode slurry is about1,000 mPa·s, about 2,000 mPa·s, about 3,000 mPa·s, about 4,000 mPa·s,about 5,000 mPa·s, about 6,000 mPa·s, about 7,000 mPa·s, or about 8,000mPa·s. Thus, the resultant slurry can be fully mixed or homogeneous.

At an alkaline pH, surface chemistry of the cathode active material maychange, thereby affecting dispersion homogeneity and particle sizedistribution of the electrode components (e.g., the cathode activematerial and conductive agent) in the cathode slurry.

The cathode slurry disclosed herein has a small D50, and a uniform andnarrow particle size distribution. FIG. 2 depicts the D50 size ofcathode active material particles in an NMP-based slurry and abase-treated slurry of the present invention respectively. It can beseen that the D50 of the NMP-based slurry is rather large and fluctuatessignificantly, while the D50 of the base-treated slurry remains smalland constant over time. This shows that the particles of thebase-treated slurry of the present invention do not agglomerate or breakapart over time, so the slurry maintains a high and stable level ofdispersion even after a long period of storage. This not only improvesthe lifespan of the lithium-ion batteries made therefrom, but alsoimproves production efficiency as slurries can be used long after beingprepared without fear of any changes in the dispersion of the slurryparticles.

In some embodiments, the cathode slurry of the present invention has aparticle size D50 in the range from about 1 μm to about 20 μm, fromabout 1 μm to about 18 μm, from about 1 μm to about 15 μm, from about 1μm to about 12 μm, from about 1 μm to about 10 μm, from about 1 μm toabout 8 μm, from about 1 μm to about 6 μm, from about 3 μm to about 20μm, from about 3 μm to about 18 μm, from about 3 μm to about 15 μm, fromabout 3 μm to about 12 μm, from about 3 μm to about 10 μm, from about 3μm to about 8 μm, from about 3 μm to about 6 μm, from about 4 μm toabout 15 μm, from about 4 μm to about 12 μm, from about 4 μm to about 10μm, from about 4 μm to about 8 μm, from about 4 μm to about 6 μm, fromabout 6 μm to about 20 μm, from about 6 μm to about 18 μm, from about 6μm to about 15 μm, from about 6 μm to about 12 μm, from about 6 μm toabout 10 μm, from about 6 μm to about 8 μm, from about 6 μm to about 15μm, from about 8 μm to about 15 μm, from about 8 μm to about 12 μm, fromabout 8 μm to about 10 μm, from about 10 μm to about 20 μm, from about10 μm to about 18 μm, from about 10 μm to about 15 μm, from about 10 μmto about 12 μm, from about 11 μm to about 20 μm, from about 11 μm toabout 18 μm, or from about 11 μm to about 15 μm. In certain embodiments,the particle diameter D50 of the cathode active material is less than 20μm, less than 18 μm, less than 15 μm, less than 12 μm, less than 10 μm,less than 8 μm, less than 7 μm, less than 6 μm, less than 5 μm, lessthan 4 μm or less than 3 μm. In some embodiments, the particle diameterD50 of the cathode active material is greater than 1 μm, greater than 2μm, greater than 3 μm, greater than 4 μm, greater than 5 μm, greaterthan 6 μm, greater than 8 μm, greater than 10 μm, or greater than 11 μm.

In conventional methods of preparing cathode slurry, a dispersing agentmay be used to assist in dispersing the cathode active material,conductive agent and binder material in the slurry. Some non-limitingexamples of the dispersing agent include a polymeric acid and asurfactant that can lower the surface tension between a liquid and asolid. In some embodiments, the dispersing agent is a nonionicsurfactant, an anionic surfactant, a cationic surfactant, an amphotericsurfactant, or a combination thereof.

One of the advantages of the present invention is that the slurrycomponents can be dispersed homogeneously at room temperature withoutthe use of a dispersing agent. In some embodiments, the method of thepresent invention does not comprise a step of adding a dispersing agentto the first suspension, second suspension, third suspension or thehomogenized cathode slurry. In certain embodiments, each of the firstsuspension, the second suspension, third suspension and the homogenizedcathode slurry is independently free of a dispersing agent.

Some non-limiting examples of the polymeric acid include polylacticacid, polysuccinic acid, polymaleic acid, pyromucic acid, polyfumaricacid, polysorbic acid, polylinoleic acid, polylinolenic acid,polyglutamic acid, polymethacrylic acid, polylicanic acid, polyglycolicacid, polyaspartic acid, polyamic acid, polyformic acid, polyaceticacid, polypropionic acid, polybutyric acid, polysebacic acid, copolymersthereof, and combinations thereof. In certain embodiments, thehomogenized cathode slurry is free of a polymeric acid.

Some non-limiting examples of suitable nonionic surfactants include acarboxylic ester, a polyethylene glycol ester, and combinations thereof.

Some non-limiting examples of suitable anionic surfactants include asalt of an alkyl sulfate, an alkyl polyethoxylate ether sulfate, analkyl benzene sulfonate, an alkyl ether sulfate, a sulfonate, asulfosuccinate, a sarcosinate, and combinations thereof. In someembodiments, the anionic surfactant comprises a cation selected from thegroup consisting of sodium, potassium, ammonium, and combinationsthereof. In certain embodiments, the anionic surfactant is sodiumdodecylbenzene sulfonate, sodium stearate, lithium dodecyl sulfate, or acombination thereof. In some embodiments, the homogenized cathode slurryis free of an anionic surfactant.

Some non-limiting examples of suitable cationic surfactant include anammonium salt, a phosphonium salt, an imidazolium salt, a sulfoniumsalt, and combinations thereof. Some non-limiting examples of suitableammonium salt include stearyl trimethylammonium bromide (STAB), cetyltrimethylammonium bromide (CTAB), myristyl trimethylammonium bromide(MTAB), trimethylhexadecyl ammonium chloride, and combinations thereof.In some embodiments, the homogenized cathode slurry is free of acationic surfactant.

Some non-limiting examples of suitable amphoteric surfactant aresurfactants that contain both cationic and anionic groups. The cationicgroup is ammonium, phosphonium, imidazolium, sulfonium, or a combinationthereof. The anionic hydrophilic group is carboxylate, sulfonate,sulfate, phosphonate, or a combination thereof. In some embodiments, thehomogenized cathode slurry is free of the amphoteric surfactant.

After uniform mixing of slurry components, the homogenized cathodeslurry can be applied on a current collector to form a coated film onthe current collector, followed by drying in step 104. The currentcollector acts to collect electrons generated by electrochemicalreactions of the cathode active material or to supply electrons requiredfor the electrochemical reactions. In some embodiments, the currentcollector can be in the form of a foil, sheet or film. In certainembodiments, the current collector is stainless steel, titanium, nickel,aluminum, copper, or alloys thereof or electrically-conductive resin. Incertain embodiments, the current collector has a two-layered structurecomprising an outer layer and an inner layer, wherein the outer layercomprises a conductive material and the inner layer comprises aninsulating material or another conductive material; for example,aluminum mounted with a conductive resin layer or a polymeric insulatingmaterial coated with an aluminum film. In some embodiments, the currentcollector has a three-layered structure comprising an outer layer, amiddle layer and an inner layer, wherein the outer and inner layerscomprise a conductive material and the middle layer comprises aninsulating material or another conductive material; for example, aplastic substrate coated with a metal film on both sides. In certainembodiments, each of the outer layer, middle layer and inner layer isindependently stainless steel, titanium, nickel, aluminum, copper, oralloys thereof or electrically-conductive resin. In some embodiments,the insulating material is a polymeric material selected from the groupconsisting of polycarbonate, polyacrylate, polyacrylonitrile, polyester,polyamide, polystyrene, polyurethane, polyepoxy, poly(acrylonitrilebutadiene styrene), polyimide, polyolefin, polyethylene, polypropylene,polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, polyether,polyphenylene oxide, cellulose polymer and combinations thereof. Incertain embodiments, the current collector has more than three layers.In some embodiments, the current collector is coated with a protectivecoating. In certain embodiments, the protective coating comprises acarbon-containing material. In some embodiments, the current collectoris not coated with a protective coating.

One undesirable reaction that occurs to a nickel-containing cathodeactive material in an aqueous slurry is lithium ions leaching from thesurface of the cathode active material and reacting with water to formLiOH. The leaching of lithium ions causes changes in the cathode activematerial, resulting in reduced performance of the battery cell madetherefrom. Therefore, lithium ion leaching is a major obstacle toapplying water-based methods to cathode slurry preparation, especiallyfor nickel-containing cathode active materials.

It has been discovered that by treating the cathode active material in anitrogen-containing base helps minimize leaching of lithium ions in thecathode slurry. FIG. 3 is a graph showing the relationship between theconcentration of lithium ions in the cathode slurry and time. Theconcentration of lithium ions measured in a slurry that has beenprepared by the method disclosed herein is substantially less than thatof an untreated cathode active material. The method disclosed hereinimproves stability of cathode active materials in aqueous slurries andeffectively reduces the amount of the lithium ions leached.

In some embodiments, the lithium ion concentration in the cathode slurryis in the range from about 300 parts per million (ppm) to about 800 ppm,from about 350 ppm to about 800 ppm, from about 400 ppm to about 800ppm, from about 500 ppm to about 800 ppm, from about 600 ppm to about800 ppm, from about 700 ppm to about 800 ppm, from about 300 ppm toabout 750 ppm, from about 300 ppm to about 700 ppm, from about 300 ppmto about 600 ppm, from about 300 ppm to about 500 ppm, from about 300ppm to about 400 ppm, from about 300 ppm to about 350 ppm, from about400 ppm to about 700 ppm, or from about 500 ppm to about 600 ppm, basedon the total weight of the cathode slurry. In some embodiments, thelithium ion concentration in the cathode slurry is more than 300 ppm,more than 350 ppm, more than 400 ppm, more than 500 ppm, or more than600 ppm, based on the total weight of the cathode slurry. In someembodiments, the lithium ion concentration is less than 800 ppm, lessthan 750 ppm, less than 700 ppm, less than 600 ppm, or less than 500ppm, based on the total weight of the cathode slurry. In someembodiments, the lithium ion concentration in the cathode slurry isabout 300 ppm, about 350 ppm, about 400 ppm, about 450 ppm, about 500ppm, about 550 ppm, about 600 ppm, about 650 ppm, about 700 ppm, about750 ppm, or about 800 ppm, based on the total weight of the cathodeslurry.

In certain embodiments, the thickness of each of the cathode and anodeelectrode layers on the current collector is independently from about 10μm to about 90 μm, from about 15 μm to about 90 μm, from about 20 μm toabout 90 μm, from about 25 μm to about 90 μm, from about 25 μm to about80 μm, from about 25 μm to about 75 μm, from about 25 μm to about 50 μm,from about 30 μm to about 90 μm, from about 30 μm to about 80 μm, fromabout 35 μm to about 90 μm, from about 35 μm to about 85 μm, from about35 μm to about 80 μm, or from about 35 μm to about 75 μm. In someembodiments, the thickness of the electrode layer on the currentcollector is about 25 μm, about 30 μm, about 35 μm, about 40 μm, about45 μm, about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm,or about 75 μm.

In some embodiments, the surface density of each of the cathode andanode electrode layers on the current collector is independently fromabout 1 mg/cm² to about 40 mg/cm², from about 1 mg/cm² to about 35mg/cm², from about 1 mg/cm² to about 30 mg/cm², from about 1 mg/cm² toabout 25 mg/cm², from about 1 mg/cm² to about 15 mg/cm², from about 3mg/cm² to about 40 mg/cm², from about 3 mg/cm² to about 35 mg/cm², fromabout 3 mg/cm² to about 30 mg/cm², from about 3 mg/cm² to about 25mg/cm², from about 3 mg/cm² to about 20 mg/cm², from about 3 mg/cm² toabout 15 mg/cm², from about 5 mg/cm² to about 40 mg/cm², from about 5mg/cm² to about 35 mg/cm², from about 5 mg/cm² to about 30 mg/cm², fromabout 5 mg/cm² to about 25 mg/cm², from about 5 mg/cm² to about 20mg/cm², from about 5 mg/cm² to about 15 mg/cm², from about 8 mg/cm² toabout 40 mg/cm², from about 8 mg/cm² to about 35 mg/cm², from about 8mg/cm² to about 30 mg/cm², from about 8 mg/cm² to about 25 mg/cm², fromabout 8 mg/cm² to about 20 mg/cm², from about 10 mg/cm² to about 40mg/cm², from about 10 mg/cm² to about 35 mg/cm², from about 10 mg/cm² toabout 30 mg/cm², from about 10 mg/cm² to about 25 mg/cm², from about 10mg/cm² to about 20 mg/cm², from about 15 mg/cm² to about 40 mg/cm², orfrom about 20 mg/cm² to about 40 mg/cm².

In some embodiments, a conductive layer can be coated on an aluminumcurrent collector to improve its current conductivity. In certainembodiments, the conductive layer comprises a material selected from thegroup consisting of carbon, carbon black, graphite, expanded graphite,graphene, graphene nanoplatelets, carbon fibers, carbon nano-fibers,graphitized carbon flake, carbon tubes, carbon nanotubes, activatedcarbon, mesoporous carbon, and combinations thereof. In someembodiments, the conductive agent is not carbon, carbon black, graphite,expanded graphite, graphene, graphene nanoplatelets, carbon fibers,carbon nano-fibers, graphitized carbon flake, carbon tubes, carbonnanotubes, activated carbon, or mesoporous carbon.

In some embodiments, the conductive layer has a thickness from about 0.5μm to about 5.0 μm. Thickness of the conductive layer will affect thevolume occupied by the current collector within a battery and the amountof the electrode material and hence the capacity in the battery.

In certain embodiments, the thickness of the conductive layer on thecurrent collector is from about 0.5 μm to about 4.5 μm, from about 1.0μm to about 4.0 μm, from about 1.0 μm to about 3.5 μm, from about 1.0 μmto about 3.0 μm, from about 1.0 μm to about 2.5 μm, from about 1.0 μm toabout 2.0 μm, from about 1.1 μm to about 2.0 μm, from about 1.2 μm toabout 2.0 μm, from about 1.5 μm to about 2.0 μm, from about 1.8 μm toabout 2.0 μm, from about 1.0 μm to about 1.8 μm, from about 1.2 μm toabout 1.8 μm, from about 1.5 μm to about 1.8 μm, from about 1.0 μm toabout 1.5 μm, or from about 1.2 to about 1.5 μm. In some embodiments,the thickness of the conductive layer on the current collector is lessthan 4.5 μm, less than 4.0 μm, less than 3.5 μm, less than 3.0 μm, lessthan 2.5 μm, less than 2.0 μm, less than 1.8 μm, less than 1.5 μm, orless than 1.2 μm. In some embodiments, the thickness of the conductivelayer on the current collector is more than 1.0 μm, more than 1.2 μm,more than 1.5 μm, more than 1.8 μm, more than 2.0 μm, more than 2.5 μm,more than 3.0 μm, or more than 3.5 μm.

FIGS. 4a and 4b depict the appearance of the surface of cathodeelectrode layers formed respectively by an untreated slurry and abase-treated slurry in accordance with the present invention. FIG. 4ashows pinholes of different size distributed across the surface of theelectrode layer, while FIG. 4b shows a smooth, continuous electrodelayer. Such pinholes lead to inferior electrochemical performance, suchas lower discharge capacities and poor cycle life, compared withelectrodes prepared by the present invention. The improved surfacemorphology of the electrode layer provided by the present inventionleads to better electrochemical performance of the battery createdtherefrom. Battery performance data is also presented below, which showsthe enhanced performance achieved when using electrodes produced inaccordance with the present invention.

In addition, the cathode prepared by the present invention exhibitsstrong adhesion of the electrode layer to the current collector. It isimportant for the electrode layer to have good peeling strength to thecurrent collector as this prevents delamination or separation of theelectrode, which would greatly influence the mechanical stability of theelectrodes and the cyclability of the battery. Therefore, the electrodesshould have sufficient peeling strength to withstand the rigors ofbattery manufacture.

FIG. 5 is a bar graph showing the peeling strengths of cathodes coatedrespectively with an organic slurry, an aqueous slurry comprisinguntreated cathode active material and an aqueous slurry preparedaccording to the present invention. The graph shows an increase in thepeeling strength of the coated film to the current collector for theelectrode prepared by the method disclosed herein.

In some embodiments, the peeling strength between the current collectorand the electrode layer is in the range from about 1.0 N/cm to about 3.0N/cm, from about 1.2 N/cm to about 3.0 N/cm, from about 1.5 N/cm toabout 3.0 N/cm, from about 1.8 N/cm to about 3.0 N/cm, from about 2.0N/cm to about 3.0 N/cm, from about 2.2 N/cm to about 3.0 N/cm, fromabout 2.5 N/cm to about 3.0 N/cm, from about 1.0 N/cm to about 2.5 N/cm,from about 1.2 N/cm to about 2.5 N/cm, from about 1.5 N/cm to about 2.5N/cm, from about 1.8 N/cm to about 2.5 N/cm, from about 2.0 N/cm toabout 2.5 N/cm, from about 1.0 N/cm to about 2.0 N/cm, from about 1.2N/cm to about 2.0 N/cm, or from about 1.5 N/cm to about 2.0 N/cm. Insome embodiments, the peeling strength between the current collector andthe electrode layer is 1.0 N/cm or more, 1.2 N/cm or more, 1.5 N/cm ormore, 2.0 N/cm or more, 2.2 N/cm or more, or 2.5 N/cm or more. In someembodiments the peeling strength between the current collector and theelectrode layer is less than 3.0 N/cm, less than 2.8 N/cm, less than 2.5N/cm, less than 2.2 N/cm, less than 2.0 N/cm, less than 1.8 N/cm, orless than 1.5 N/cm.

Table 4 below shows ICP mass spectroscopy data of diluted slurries ofNMC811 that was pre-treated with ammonia at various concentrations. Thedata demonstrates that less lithium from the cathode active material isdissolved in the solvent when the cathode active material ispre-treated, thus showing that the pre-treatment of the presentinvention can inhibit loss of lithium from the cathode active material.It can be seen that the inhibition of lithium loss of the cathode activematerial is correlated with the concentration of the ammonia used.

In some embodiments, the lithium loss of the cathode active material isinhibited by a percentage between about 1 percent and about 50 percent,relative to the lithium loss of the cathode material in pure water. Incertain embodiments, the lithium loss of the cathode active material isinhibited by a percentage between about 5 percent and about 50 percent,between about 10 percent and about 50 percent, between about 15 percentand about 50 percent, between about 20 percent and about 50 percent,between about 25 percent and about 50 percent, between about 1 percentand about 45 percent, between about 5 percent and about 45 percent,between about 10 percent and about 45 percent, between about 15 percentand about 45 percent, between about 20 percent and about 45 percent,between about 25 percent and about 45 percent, between about 1 percentand about 40 percent, between about 5 percent and about 40 percent,between about 10 percent and about 40 percent, between about 15 percentabout and 40 percent, between about 20 percent and about 40 percent,between about 1 percent and about 35 percent, between about 5 percentand about 35 percent, between about 10 percent and about 35 percent,between about 15 percent and about 35 percent, between about 20 percentand about 35 percent, between about 1 percent and about 30 percent,between about 5 percent and about 30 percent, between about 10 percentand about 30 percent, between about 15 percent and about 30 percent,between about 1 percent and about 20 percent, between about 3 percentand about 20 percent, between about 5 percent and about 20 percent,between about 8 percent and about 20 percent, between about 10 percentand about 20 percent, between about 1 percent and about 15 percent, orabout between 1 percent and about 10 percent, relative to the lithiumloss of the cathode active material in pure water. In some embodiments,the lithium loss of the cathode active material is inhibited by apercentage of about 1 percent or above, about 3 percent or above, about5 percent or above, about 8 percent or above, about 10 percent or above,about 12 percent or above, about 15 percent or above, about 18 percentor above, about 20 percent or above, about 25 percent or above, or about30 percent or above, relative to the lithium loss of the cathode activematerial in pure water. In some embodiments, the lithium loss of thecathode active material is inhibited by a percentage of about 50 percentor below, about 45 percent or below, about 40 percent or below, about 35percent or below, about 30 percent or below, about 25 percent or below,about 20 percent or below, about 15 percent or below, about 10 percentor below, or about 5 percent or below, relative to the lithium loss ofthe cathode active material in pure water.

During coating, pH is a very important parameter in controlling theslurry's stability as it affects key properties of the slurry, such asviscosity and degree of dispersion. If the slurry pH changes, then suchkey properties will also change. The risk of pH instability causes aneed to coat the slurry on the current collector immediately afterhomogenization. This is very difficult to realize under mass productionconditions, where the coating processes often continue for many hours.Any fluctuations in the key properties during coating are a severe issueand will make the coating process unstable. One benefit of the presentinvention is that the slurry pH, and thus the key properties, remainstable during homogenization and also for a long time afterhomogenization. It is found that the pH of the slurry disclosed hereinremains relatively constant during extended stagnant storage of up totwo weeks, while the pH of conventional water-based slurries risessignificantly during storage. The stability of the pH allows the slurrydisclosed herein to remain homogenous and uniform during such extendedstorage, allowing sufficient time for transportation of the slurry toproceed to the coating process.

The cathode slurry can be obtained by homogenizing the third suspensionfor a time period from about 10 minutes to about 6 hours, from about 1hour to about 6 hours, from about 2 hours to about 6 hours, from about 4hours to about 6 hours, from about 10 minutes to about 5 hours, fromabout 1 hour to about 5 hours, from about 3 hours to about 5 hours, fromabout 10 minutes to about 4 hours, from about 1 hour to about 4 hours,from about 2 hours to about 4 hours, from about 10 minutes to about 3hours, from about 1 hour to about 3 hours, from about 2 hours to about 3hours, from about 10 minutes to about 2 hours, from about 30 minutes toabout 2 hours, from about 1 hour to about 2 hours, from about 10 minutesto about 1 hour, from about 30 minutes to about 1 hour, or from about 10minutes to about 30 minutes.

In some embodiments, the concentration of the base in the cathode slurryis from about 0.5% to about 3.5%, from about 0.5% to about 3.0%, fromabout 0.5% to about 2.5%, from about 0.5% to about 2.0%, from about 0.5%to about 1.75%, from about 0.5% to about 1.6%, from about 0.5% to about1.5%, or from about 0.5% to about 1.25%, based on the total weight ofthe cathode slurry.

In some embodiments, the amount of the cathode active material is fromabout 10% to about 80%, from about 10% to about 70%, from about 10% toabout 60%, from about 10% to about 50%, from about 10% to about 40%,from about 10% to about 30%, from about 10% to about 20%, from about 25%to about 80%, from about 25% to about 70%, from about 25% to about 60%,from about 25% to about 50%, from about 25% to about 40%, from about 30%to about 70%, from about 30% to about 60%, from about 30% to about 50%,from about 30% to about 40%, from about 40% to about 80%, from about 35%to about 65%, from about 35% to about 50%, from about 35% to about 45%,from about 40% to about 70%, from about 40% to about 60%, from about 40%to about 50%, from about 45% to about 80%, from about 45% to about 70%,from about 45% to about 60%, from about 45% to about 50%, from about 50%to about 80%, from about 50% to about 70%, from about 50% to about 60%,from about 60% to about 80%, or from about 60% to about 70%, by weightor volume, based on the total weight or volume of the cathode slurry. Incertain embodiments, the amount of the cathode active material is atleast 10%, at least 15%, at least 20%, at least 25%, at least 27.5%, atleast 30%, at least 32.5%, at least 35%, at least 37.5%, at least 40%,at least 42.5%, at least 45%, at least 47.5%, at least 50%, at least52.5%, at least 55%, at least 57.5, at least 60%, at least 65%, at least70%, or at least 75% by weight or volume, based on the total weight orvolume of the cathode slurry. In certain embodiments, the amount of thecathode active material is at most 25%, at most 27.5%, at most 30%, atmost 32.5%, at most 35%, at most 37.5%, at most 40%, at most 42.5%, atmost 45%, at most 47.5%, at most 50%, at most 52.5%, at most 55%, atmost 57.5%, at most 60%, at most 65%, at most 70%, or at most 75% byweight or volume, based on the total weight or volume of the cathodeslurry.

The slurry should maintain a stable pH during homogenization, as anunstable pH can significantly reduce the lifetime of the battery. Ingeneral, when the cathode active material is pre-treated in a base, theslurry pH was found to decrease slightly during homogenization. Incertain embodiments, the decrease in pH observed during homogenizationis from about 0.1 pH units to about 1.0 pH unit, from about 0.1 pH unitsto about 0.8 pH units, from about 0.1 pH units to about 0.6 pH units,from about 0.1 pH units to about 0.5 pH units, from about 0.1 pH unitsto about 0.4 pH units, or from about 0.1 pH units to about 0.3 pH units.In certain embodiments, the decrease in pH observed duringhomogenization is less than 1.0 pH unit, less than 0.8 pH units, lessthan 0.6 pH units, less than 0.5 pH units, less than 0.45 pH units, lessthan 0.4 pH units, less than 0.35 pH units, less than 0.3 pH units, lessthan 0.2 pH units, or less than 0.1 pH units.

The thickness of the current collector affects the volume it occupieswithin the battery, the amount of the electrode active material needed,and hence the capacity in the battery. In some embodiments, the currentcollector has a thickness from about 5 μm to about 30 μm. In certainembodiments, the current collector has a thickness from about 5 μm toabout 20 μm, from about 5 μm to about 15 μm, from about 10 μm to about30 μm, from about 10 μm to about 25 μm, or from about 10 μm to about 20μm.

In certain embodiments, the coating process is performed using a doctorblade coater, a slot-die coater, a transfer coater, a spray coater, aroll coater, a gravure coater, a dip coater, or a curtain coater.

Evaporating the solvent to create a dry porous electrode is needed tofabricate the battery. After applying the homogenized cathode slurry ona current collector, the coated film on the current collector can bedried by a dryer to obtain the battery electrode. Any dryer that can drythe coated film on the current collector can be used herein. Somenon-limiting examples of the dryer include a batch drying oven, aconveyor drying oven, and a microwave drying oven. Some non-limitingexamples of the conveyor drying oven include a conveyor hot air dryingoven, a conveyor resistance drying oven, a conveyor inductive dryingoven, and a conveyor microwave drying oven.

In some embodiments, the conveyor drying oven for drying the coated filmon the current collector includes one or more heating sections, whereineach of the heating sections is individually temperature-controlled, andwherein each of the heating sections may include independentlycontrolled heating zones.

In certain embodiments, the conveyor drying oven comprises a firstheating section positioned on one side of the conveyor and a secondheating section positioned on an opposing side of the conveyor from thefirst heating section, wherein each of the first and second heatingsections independently comprises one or more heating elements and atemperature control system connected to the heating elements of thefirst heating section and the second heating section in a manner tomonitor and selectively control the temperature of each heating section.

In some embodiments, the conveyor drying oven comprises a plurality ofheating sections, wherein each heating section includes independentheating elements that are operated to maintain a constant temperaturewithin the heating section.

In certain embodiments, each of the first and second heating sectionsindependently has an inlet heating zone and an outlet heating zone,wherein each of the inlet and outlet heating zones independentlycomprises one or more heating elements and a temperature control systemconnected to the heating elements of the inlet heating zone and theoutlet heating zone in a manner to monitor and selectively control thetemperature of each heating zone separately from the temperature controlof the other heating zones.

The coated film on the current collector should be dried at atemperature of approximately 75° C. or less in approximately 20 minutesor less. Drying the coated positive electrode at temperatures above 75°C. may result in undesirable deformation of the cathode, thus affectingthe performance of the positive electrode.

In some embodiments, the coated film on the current collector can bedried at a temperature from about 25° C. to about 75° C. In certainembodiments, the coated film on the current collector can be dried at atemperature from about 25° C. to about 70° C., from about 25° C. toabout 65° C., about 25° C. to about 60° C., about 25° C. to about 55°C., about 25° C. to about 50° C., about 25° C. to about 45° C., about25° C. to about 40° C., from about 30° C. to about 75° C., from about30° C. to about 70° C., from about 30° C. to about 65° C., from about30° C. to about 60° C., from about 30° C. to about 55° C., from about30° C. to about 50° C., from about 35° C. to about 75° C., from about35° C. to about 70° C., from about 35° C. to about 65° C., from about35° C. to about 60° C., from about 40° C. to about 75° C., from about40° C. to about 70° C., from about 40° C. to about 65° C., or from about40° C. to about 60° C. In some embodiments, the coated film on thecurrent collector is dried at a temperature less than 75° C., less than70° C., less than 65° C., less than 60° C., less than 55° C., or lessthan 50° C. In some embodiments, the coated film on the currentcollector is dried at a temperature of higher than about 70° C., higherthan about 65° C., higher than about 60° C., higher than about 55° C.,higher than about 50° C., higher than about 45° C., higher than about40° C., or higher than about 35° C., higher than about 30° C., or higherthan about 25° C.

In certain embodiments, the conveyor moves at a speed from about 1meter/minute to about 120 meters/minute, from about 1 meter/minute toabout 100 meters/minute, from about 1 meter/minute to about 80meters/minute, from about 1 meter/minute to about 60 meters/minute, fromabout 1 meter/minute to about 40 meters/minute, from about 10meters/minute to about 120 meters/minute, from about 10 meters/minute toabout 80 meters/minute, from about 10 meters/minute to about 60meters/minute, from about 10 meters/minute to about 40 meters/minute,from about 25 meters/minute to about 120 meters/minute, from about 25meters/minute to about 100 meters/minute, from about 25 meters/minute toabout 80 meters/minute, from about 25 meters/minute to about 60meters/minute, from about 50 meters/minute to about 120 meters/minute,from about 50 meters/minute to about 100 meters/minute, from about 50meters/minute to about 80 meters/minute, from about 75 meters/minute toabout 120 meters/minute, from about 75 meters/minute to about 100meters/minute, from about 2 meters/minute to about 25 meters/minute,from about 2 meters/minute to about 20 meters/minute, from about 2meters/minute to about 16 meters/minute, from about 3 meters/minute toabout 30 meters/minute, from about 3 meters/minute to about 20meters/minute, or from about 3 meters/minute to about 16 meters/minute.

Controlling the conveyor length and speed can regulate the drying timeof the coated film. In some embodiments, the coated film on the currentcollector can be dried for a time period from about 2 minutes to about20 minutes, from about 2 minutes to about 17 minutes, from about 2minutes to about 15 minutes, from about 2 minutes to about 14 minutes,from about 2 minutes to about 10 minutes, from about 2 minutes to about11 minutes, from about 2 minutes to about 8 minutes, from about 5minutes to about 20 minutes, from about 5 minutes to about 11 minutes,from about 5 minutes to about 14 minutes, from about 5 minutes to about17 minutes, or from about 5 minutes to about 10 minutes. In certainembodiments, the coated film on the current collector can be dried for atime period of less than 5 minutes, less than 8 minutes, less than 10minutes, less than 11 minutes, less than 14 minutes, less than 17minutes, or less than 20 minutes. In some embodiments, the coated filmon the current collector can be dried for a time period of about 5minutes, about 8 minutes, about 10 minutes, about 11 minutes, about 14minutes, about 17 minutes, or about 20 minutes.

The method disclosed herein has the advantage that aqueous solvents canbe used in the manufacturing process, which can save on processing timeand equipment, as well as improve safety by eliminating the need tohandle or recycle hazardous organic solvents. Since aqueous solvents areused in the present invention, the electrode would require less time andenergy to dry. In addition, costs are reduced by simplifying the overallprocess. Therefore, this method is especially suited for industrialprocesses because of its low cost and ease of handling.

As described above, by treating the cathode active material with thebase disclosed herein, the slurry preparation method disclosed hereinhas a controlled cathode slurry pH, favorably enhancing the slurry'sstability. The development of water-based cathode slurries withoutlowering the battery performance such as cyclability and capacity isachieved by the present invention. Batteries comprising positiveelectrodes prepared in accordance with the present invention show highcycle stability. In addition, the low drying temperatures and decreaseddrying times of the coated film significantly improve performance of thebatteries.

The electrode assembly comprises at least one cathode, at least oneanode and at least one separator placed in between the cathode andanode. Also provided herein is an electrode assembly comprising acathode prepared by the method described above.

In certain embodiments, the electrode assembly is dried after beingassembled to reduce its water content. In other embodiments, at leastone of the components of the electrode assembly is dried before theelectrode assembly is assembled. In some embodiments, at least one ofthe components is pre-dried before assembly of the electrode assembly.In certain embodiments, the separator is pre-dried before beingassembled to the electrode assembly.

It is not necessary to dry the separator to a very low water content.The remaining water content of the pre-dried separator can be furtherreduced by the subsequent drying step. In some embodiments, the watercontent in the pre-dried separator is from about 50 ppm to about 800ppm, from about 50 ppm to about 700 ppm, from about 50 ppm to about 600ppm, from about 50 ppm to about 500 ppm, from about 50 ppm to 400 ppm,from about 50 ppm to about 300 ppm, from about 50 ppm to 200 ppm, fromabout 50 ppm to 100 ppm, from about 100 ppm to about 500 ppm, from about100 ppm to about 400 ppm, from about 100 ppm to about 300 ppm, fromabout 100 ppm to about 200 ppm, from about 200 ppm to about 500 ppm,from about 200 ppm to about 400 ppm, from about 300 ppm to about 800ppm, from about 300 ppm to about 600 ppm, from about 300 ppm to about500 ppm, from about 300 ppm to about 400 ppm, from about 400 ppm toabout 800 ppm, or from about 400 ppm to about 500 ppm, based on thetotal weight of the pre-dried separator. In some embodiments, the watercontent in the pre-dried separator is less than 500 ppm, less than 400ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, or lessthan 50 ppm by weight, based on the total weight of the pre-driedseparator.

In certain embodiments, the dried electrode assembly may have a watercontent from about 20 ppm to 350 ppm, from about 20 ppm to 300 ppm, fromabout 20 ppm to 250 ppm, from about 20 ppm to 200 ppm, from about 20 ppmto about 100 ppm, from about 20 ppm to about 50 ppm, from about 50 ppmto about 350 ppm, from about 50 ppm to about 250 ppm, from about 50 ppmto about 150 ppm, from about 100 ppm to about 350 ppm, from about 100ppm to about 300 ppm, from about 100 ppm to about 250 ppm, from about100 ppm to about 200 ppm, from about 100 ppm to about 150 ppm, fromabout 150 ppm to about 350 ppm, from about 150 ppm to about 300 ppm,from about 150 ppm to about 250 ppm, from about 150 ppm to about 200ppm, from about 200 ppm to about 350 ppm, from about 250 ppm to about350 ppm, or from about 300 ppm to about 350 ppm, based on the totalweight of the dried electrode assembly.

In some embodiments, the dried separator may have a water content fromabout 50 ppm to about 500 ppm, from about 50 ppm to 400 ppm, from about50 ppm to about 300 ppm, from about 50 ppm to 200 ppm, from about 50 ppmto 100 ppm, from about 100 ppm to about 500 ppm, from about 100 ppm toabout 300 ppm, from about 200 ppm to about 500 ppm, from about 300 ppmto about 500 ppm, or from about 400 ppm to about 500 ppm, based on thetotal weight of the dried separator.

FIG. 6 shows the discharge curves of three batteries comprising acathode prepared respectively using an NMP-based slurry, an aqueousslurry containing untreated cathode active material and an aqueousslurry containing base-treated cathode active material in accordancewith the present invention. As illustrated in the graph, the batterywith the base-treated aqueous slurry of the present invention exhibitsbetter discharging performance than the battery with the conventionaluntreated aqueous slurry. This result provides further evidence that thebase-treated slurry preparation method of the present inventionsignificantly improves the electrochemical performance of the battery.Furthermore, it is evident that the method disclosed in this inventionis advantageous over the conventional water-based method.

When compared to the battery with the NMP-based slurry, the battery withthe base-treated aqueous slurry of the present invention exhibits asimilar discharge performance, as shown in FIG. 6. However, by usingaqueous solvents and water-soluble materials, the method of the presentinvention reduces the environmental impact of the manufacturing process,as well as lowers production cost as water-soluble materials aregenerally less expensive and require fewer specialized equipment tohandle. Therefore, the present invention can produce lithium-ionbatteries more cheaply and in a more environmentally-friendly waywithout sacrificing battery performance.

The following examples are presented to exemplify embodiments of theinvention but are not intended to limit the invention to the specificembodiments set forth. Unless indicated to the contrary, all parts andpercentages are by weight. All numerical values are approximate. Whennumerical ranges are given, it should be understood that embodimentsoutside the stated ranges may still fall within the scope of theinvention. Specific details described in each example should not beconstrued as necessary features of the invention.

EXAMPLES

The pH value of the slurry was measured by an electrode-type pH meter(ION 2700, Eutech Instruments). The viscosity of slurry was measuredusing a rotational viscosity meter (NDJ-5S, Shanghai JT ElectronicTechnology Co. Ltd., China).

The peeling strengths of the dried electrode layers were measured by atensile testing machine (DZ-106A, obtained from Dongguan Zonhow TestEquipment Co. Ltd., China). This test measures the average forcerequired to peel an electrode layer from the current collector at 1800angle in Newtons per 18 mm width of the test sample. A strip of adhesiontape (3M; US; model no. 810) with a width of 18 mm was attached onto thesurface of the cathode electrode layer. The cathode strip was clippedonto the testing machine and the tape was folded back on itself at 180degrees, and placed in a moveable jaw and pulled at room temperature anda peel rate of 200 mm per minute. The maximum stripping force measuredwas taken as the peeling strength. Measurements were repeated threetimes to find the average value.

The water content in the electrode assembly was measured by Karl-Fischertitration. The electrode assembly was cut into small pieces of 1 cm×1 cmin a glove box filled with argon gas. The cut electrode assembly havinga size of 1 cm×1 cm was weighed in a sample vial. The weighed electrodeassembly was then added into a titration vessel for Karl Fischertitration using a Karl Fischer coulometry moisture analyzer (831 KFCoulometer, Metrohm, Switzerland). Measurements were repeated threetimes to find the average value.

The water content in the separator was measured by Karl-Fischertitration. The electrode assembly was cut into small pieces of 1 cm×1 cmin a glove box filled with argon gas. The electrode assembly wasseparated into the anode, cathode and separator layers. The watercontents of the separated separator layers were analyzed by Karl Fischertitration as described above. Measurements were repeated three times tofind the average value.

Example 1 A) Preparation of Positive Electrode

1.28 g of ammonia solution (28 wt. %) was diluted with 5.87 g ofdeionized water to produce an aqueous solution at 25° C. with an ammoniaconcentration of 5 wt. %. After the addition, the aqueous solution wasfurther stirred for about 5 minutes at 25° C. Thereafter, a firstsuspension was prepared by dispersing 47 g of NMC532 (obtained fromHenan Kelong NewEnergy Co., Ltd., Xinxiang, China) in the aqueoussolution at 25° C. The first suspension was sealed and left to rest at25° C. for 30 minutes.

A second suspension was prepared by dispersing 1.5 g of conductive agent(SuperP; obtained from Timcal Ltd, Bodio, Switzerland) and 10 g ofbinder (LA138, 85% water content, Chengdu Indigo Power Sources Co.,Ltd., China) in 5.79 g of deionized water while stirring with anoverhead stirrer (R20, IKA). After the addition, the second suspensionwas further stirred for about 30 minutes at 25° C. at a speed of 1,200rpm.

A third suspension with an ammonia concentration of 0.5 wt. % wasprepared by adding the first suspension to the second suspension at 25°C. while stirring with an overhead stirrer. Then, the third suspensionwas degassed under a pressure of about 10 kPa for 1 hour. Then, thethird suspension was further stirred for about 60 minutes at 25° C. at aspeed of 1,200 rpm to form a homogenized cathode slurry.

The homogenized cathode slurry was coated onto one side of acarbon-coated aluminum foil having a thickness of 14 μm as a currentcollector using a doctor blade coater with a gap width of 60 μm. Thethickness of the carbon coating was 1 μm. The coated slurry film on thealuminum foil was dried to form a cathode electrode layer by anelectrically heated conveyor oven (TH-1A, obtained from Nanjing TonghaoDrying Equipment Co. Ltd., China) at 50° C. at a conveyor speed of about5 meters/minute. The drying time was about 6 minutes. The electrode wasthen pressed to decrease the thickness of the cathode electrode layer to35 μm.

B) Preparation of Negative Electrode

A negative electrode slurry was prepared by mixing 90 wt. % of hardcarbon (HC; purity of 99.5%, obtained from Ruifute Technology Ltd.,Shenzhen, Guangdong, China) with 1.5 wt. % carboxymethyl cellulose (CMC,BSH-12, DKS Co. Ltd., Japan) and 3.5 wt. % SBR (AL-2001, NIPPON A&LINC., Japan) as a binder, and 5 wt. % carbon black as a conductive agentin deionized water. The solid content of the anode slurry was 50 wt. %.The slurry was coated onto one side of a copper foil having a thicknessof 8 μm using a doctor blade with a gap width of about 55 μm. The coatedfilm on the copper foil was dried at about 50° C. for 2.4 minutes by ahot air dryer to obtain a negative electrode. The electrode was thenpressed to decrease the thickness of the coating to 30 μm and thesurface density was 10 mg/cm².

C) Assembling of Coin Cell

CR2032 coin-type Li cells were assembled in an argon-filled glove box.The coated cathode and anode sheets were cut into disc-form positive andnegative electrodes, which were then assembled into an electrodeassembly by stacking the cathode and anode electrode platesalternatively and then packaged in a case made of an aluminum-plasticlaminated film. The cathode and anode electrode plates were kept apartby separators and the case was pre-formed. The separator was a ceramiccoated microporous membrane made of nonwoven fabric (MPM, Japan), whichhad a thickness of about 25 μm. The electrode assembly was then dried ina box-type resistance oven under vacuum (DZF-6020, obtained fromShenzhen Kejing Star Technology Co. Ltd., China) at 105° C. for about 16hours. The water content of the separator and electrode assembly afterdrying was 200 ppm and 300 ppm respectively.

An electrolyte was then injected into the case holding the packedelectrodes under a high-purity argon atmosphere with a moisture andoxygen content of less than 3 ppm respectively. The electrolyte was asolution of LiPF₆ (1 M) in a mixture of ethylene carbonate (EC), ethylmethyl carbonate (EMC) and dimethyl carbonate (DMC) at a volume ratio of1:1:1. After electrolyte filling, the coin cell was vacuum sealed andthen mechanically pressed using a punch tooling with a standard circularshape.

D) Electrochemical Measurements

The coin cells were analyzed in a constant current mode using amulti-channel battery tester (BTS-4008-5V10 mA, obtained from NewareElectronics Co. Ltd, China). After 1 cycle at C/20 was completed, theywere charged and discharged at a rate of C/2. The charging/dischargingcycling tests of the cells were performed between 3.0 and 4.3 V at acurrent density of C/2 at 25° C. to obtain the discharge capacity. Theelectrochemical performance of the coin cell of Example 1 was measuredand is shown in Table 1 below.

Example 2

A positive electrode was prepared in the same manner as in Example 1,except that the aqueous solution was formed by diluting 2.83 g ofammonia solution (28 wt. %) with 13 g of deionized water, and the secondsuspension was prepared by mixing the binder and conductive agent in4.99 g of deionized water, so that a third suspension with an ammoniaconcentration of 1 wt. % was formed when the first suspension was addedto the second suspension.

Example 3

A positive electrode was prepared in the same manner as in Example 1,except that the aqueous solution was formed by diluting 4.87 g ofammonia solution (28 wt. %) with 22.4 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 5.14 g of deionized water, so that a third suspension with an ammoniaconcentration of 1.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 4

A positive electrode was prepared in the same manner as in Example 1,except that the aqueous solution had an ammonia concentration of 10 wt.% and was formed by diluting 2.55 g of ammonia solution (28 wt. %) with4.59 g of deionized water, and the second suspension was prepared bymixing the binder and conductive agent in 5.79 g of deionized water, sothat a third suspension with an ammonia concentration of 1 wt. % wasformed when the first suspension was added to the second suspension.

Example 5

A positive electrode was prepared in the same manner as in Example 4,except that the aqueous solution was formed by diluting 4.12 g ofammonia solution (28 wt. %) with 7.42 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 6.88 g of deionized water, so that a third suspension with an ammoniaconcentration of 1.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 6

A positive electrode was prepared in the same manner as in Example 1,except that the aqueous solution had an ammonia concentration of 2 wt. %and was formed by diluting 1.49 g of ammonia solution (28 wt. %) with19.3 g of deionized water, and the second suspension was prepared bymixing the binder and conductive agent in 4 g of deionized water, sothat a third suspension with an ammonia concentration of 0.5 wt. % wasformed when the first suspension was added to the second suspension.

Example 7

A positive electrode was prepared in the same manner as in Example 1,except that the aqueous solution had a concentration of 15 wt. % and wasformed by diluting 2.55 g of ammonia solution (28 wt. %) with 2.21 g ofdeionized water, and the second suspension was prepared by mixing thebinder and conductive agent in 8.17 g of deionized water, so that athird suspension with an ammonia concentration of 1 wt. % was formedwhen the first suspension was added to the second suspension.

Example 8

A positive electrode was prepared in the same manner as in Example 7,except that the aqueous solution was formed by diluting 3.83 g ofammonia solution (28 wt. %) with 3.32 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 5.79 g of deionized water, so that a third suspension with an ammoniaconcentration of 1.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 9

A positive electrode was prepared in the same manner as in Example 1,except that the aqueous solution was a 10 wt. % dimethylamine solutionthat was formed by diluting 0.71 g of dimethylamine solution (anhydrous;≥99% purity) with 6.43 g of deionized water, and the second suspensionwas prepared by mixing the binder and conductive agent in 5.79 g ofdeionized water, so that a third suspension with a dimethylamineconcentration of 1 wt. % was formed when the first suspension was addedto the second suspension.

Example 10

A positive electrode was prepared in the same manner as in Example 1,except that the aqueous solution was a 10 wt. % trimethylamine solutionthat was formed by diluting 0.71 g of trimethylamine solution(anhydrous; ≥99% purity) with 6.43 g of deionized water, and the secondsuspension was prepared by mixing 10 g of LA133 binder (85% watercontent; obtained from Chengdu Indigo Power Sources Co., Ltd., China)and 1.5 g of conductive agent (SuperP; obtained from Timcal Ltd, Bodio,Switzerland) in 5.79 g of deionized water, so that a third suspensionwith a trimethylamine concentration of 1 wt. % was formed when the firstsuspension was added to the second suspension.

Example 11

A positive electrode was prepared in the same manner as in Example 10,except that the aqueous solution was formed by diluting 1.15 g oftrimethylamine solution (anhydrous; ≥99% purity) with 10.4 g ofdeionized water, and the second suspension was prepared by mixing thebinder and conductive agent in 6.88 g of deionized water, so that athird suspension with a trimethylamine concentration of 1.5 wt. % wasformed when the first suspension was added to the second suspension.

Example 12

A positive electrode was prepared in the same manner as in Example 10,except that the aqueous solution was formed by diluting 1.59 g oftrimethylamine solution (anhydrous; 299% purity) with 14.3 g ofdeionized water, and the second suspension was prepared by mixing thebinder and conductive agent in 4.99 g of deionized water, so that athird suspension with a trimethylamine concentration of 2 wt. % wasformed when the first suspension was added to the second suspension.

Example 13

A positive electrode was prepared in the same manner as in Example 4,except that the 10 g of LA138 binder was replaced with polyacrylonitrile(PAN) (85% water content) of the same weight.

Example 14

A positive electrode was prepared in the same manner as in Example 4,except that the second suspension was prepared by mixing 1.5 g ofconductive agent and a 3 g mixture (50% water content) ofstyrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) in 12.8g of deionized water, wherein the weight ratio of SBR to CMC was 3 to 1.

Example 15

A positive electrode was prepared in the same manner as in Example 4,except that the second suspension was prepared by mixing 1.5 g ofconductive agent and 15 g of sodium alginate (10 wt. % solution) in 0.79g of deionized water.

Example 16

A positive electrode was prepared in the same manner as in Example 4,except that the second suspension was prepared by mixing 1.5 g ofconductive agent and 3.33 g of latex (55% water content) in 14.3 g ofdeionized water.

Example 17

A positive electrode was prepared in the same manner as in Example 4,except the homogenized cathode slurry was coated on an aluminum foilwith no carbon coating.

Comparative Example 1

A positive electrode slurry was prepared by dispersing 47 g of NMC532(obtained from Henan Kelong NewEnergy Co., Ltd., Xinxiang, China), 1.5 gof conductive agent (SuperP; obtained from Timcal Ltd, Bodio,Switzerland) and 10 g of LA138 binder (85% water content, Chengdu IndigoPower Sources Co., Ltd., China) in 5.79 g of deionized water whilestirring with an overhead stirrer. The slurry was degassed under apressure of about 10 kPa for 1 hour. Then, the slurry was furtherstirred for about 60 minutes at 25° C. at a speed of 1,200 rpm.

The homogenized cathode slurry was coated onto one side of an aluminumfoil having a thickness of 13 μm as a current collector using a doctorblade coater with a gap width of 45 μm. The coated slurry film on thealuminum foil was dried to form a cathode electrode layer by anelectrically heated conveyor oven (TH-1A, obtained from Nanjing TonghaoDrying Equipment Co. Ltd., China) at 50° C. at a conveyor speed of about5 meters/minute. The drying time was about 6 minutes. The electrode wasthen pressed to decrease the thickness of the cathode electrode layer to35 μm.

Comparative Example 2

A positive electrode slurry was prepared by dispersing 47 g of NMC532(obtained from Henan Kelong NewEnergy Co., Ltd., Xinxiang, China), 1.5 gof conductive agent (SuperP; obtained from Timcal Ltd, Bodio,Switzerland) and 15 g of polyvinylidene fluoride binder (PVDF; 10 wt. %solution in NMP; Solef® 5130, obtained from Solvay S.A., Belgium) in7.93 g of N-methyl-2-pyrrolidone (NMP; ≥99%, Sigma-Aldrich, USA) whilestirring with an overhead stirrer. The slurry was degassed under apressure of about 10 kPa for 1 hour. Then, the slurry was furtherstirred for about 60 minutes at 25° C. at a speed of 1,200 rpm.

The homogenized cathode slurry was coated onto one side of an aluminumfoil having a thickness of 13 μm as a current collector using a doctorblade coater with a gap width of 45 μm. The coated slurry film on thealuminum foil was dried to form a cathode electrode layer by anelectrically heated conveyor oven (TH-1A, obtained from Nanjing TonghaoDrying Equipment Co. Ltd., China) at 50° C. at a conveyor speed of about5 meters/minute. The drying time was about 6 minutes. The electrode wasthen pressed to decrease the thickness of the cathode electrode layer to35 μm.

Comparative Example 3

A positive electrode was prepared in the same manner as in Example 17,except that the aqueous solution was a 10 wt. % citric acid solutionthat was prepared by adding 0.71 g of citric acid into 6.43 g ofdeionized water.

Preparation of Negative Electrode of Examples 2-17 and ComparativeExamples 1-3

The negative electrodes of Examples 2-17 and Comparative Examples 1-3were prepared in the same manner as in Example 1.

Assembling of Coin Cells of Examples 2-17 and Comparative Examples 1-3

The coin cells of Examples 2-17 and Comparative Examples 1-3 wereassembled in the same manner as in Example 1.

Electrochemical Measurements of Examples 2-17 and Comparative Examples1-3

The electrochemical performance of the coin cells of Examples 2-17 andComparative Examples 1-3 was measured in the same manner as in Example 1and the test results are shown in Table 1 below.

Example 18

A positive electrode was prepared in the same manner as in Example 1,except that the 47 g of NMC532 was replaced with NMC622 (obtained fromHenan Kelong NewEnergy Co., Ltd., Xinxiang, China) of the same weight.

Example 19

A positive electrode was prepared in the same manner as in Example 18,except that the aqueous solution was formed by diluting 2.83 g ofammonia solution (28 wt. %) with 13 g of deionized water, and the secondsuspension was prepared by mixing the binder and conductive agent in4.99 g of deionized water, so that a third suspension with an ammoniaconcentration of 1 wt. % was formed when the first suspension was addedto the second suspension.

Example 20

A positive electrode was prepared in the same manner as in Example 18,except that the aqueous solution was formed by diluting 4.87 g ofammonia solution (28 wt. %) with 22.4 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 5.14 g of deionized water, so that a third suspension with an ammoniaconcentration of 1.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 21

A positive electrode was prepared in the same manner as in Example 18,except that the aqueous solution was formed by diluting 7.44 g ofammonia solution (28 wt. %) with 34.2 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 4 g of deionized water, so that a third suspension with an ammoniaconcentration of 2 wt. % was formed when the first suspension was addedto the second suspension.

Example 22

A positive electrode was prepared in the same manner as in Example 18,except that the aqueous solution had an ammonia concentration of 7 wt. %and was formed by diluting 4.25 g of ammonia solution (28 wt. %) with12.8 g of deionized water, and the second suspension was prepared bymixing the binder and conductive agent in 3.86 g of deionized water, sothat a third suspension with an ammonia concentration of 1.5 wt. % wasformed when the first suspension was added to the second suspension.

Example 23

A positive electrode was prepared in the same manner as in Example 18,except that the aqueous solution had an ammonia concentration of 10 wt.% and was formed by diluting 2.55 g of ammonia solution (28 wt. %) with4.59 g of deionized water, and the second suspension was prepared bymixing the binder and conductive agent in 5.79 g of deionized water, sothat a third suspension with an ammonia concentration of 1 wt. % wasformed when the first suspension was added to the second suspension.

Example 24

A positive electrode was prepared in the same manner as in Example 23,except that the aqueous solution was formed by diluting 4.12 g ofammonia solution (28 wt. %) with 7.42 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 6.88 g of deionized water, so that a third suspension with an ammoniaconcentration of 1.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 25

A positive electrode was prepared in the same manner as in Example 23,except that the aqueous solution was formed by diluting 5.67 g ofammonia solution (28 wt. %) with 10.2 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 4.99 g of deionized water, so that a third suspension with an ammoniaconcentration of 2 wt. % was formed when the first suspension was addedto the second suspension.

Example 26

A positive electrode was prepared in the same manner as in Example 18,except that the aqueous solution had an ammonia concentration of 13 wt.% and was formed by diluting 3.83 g of ammonia solution (28 wt. %) with4.42 g of deionized water, and the second suspension was prepared bymixing the binder and conductive agent in 4.69 g of deionized water, sothat a third suspension with an ammonia concentration of 1.5 wt. % wasformed when the first suspension was added to the second suspension.

Example 27

A positive electrode was prepared in the same manner as in Example 18,except that the aqueous solution had an ammonia concentration of 15 wt.% and was formed by diluting 2.38 g of ammonia solution (28 wt. %) with2.06 g of deionized water, and the second suspension was prepared bymixing the binder and conductive agent in 3.72 of deionized water, sothat a third suspension with an ammonia concentration of 1 wt. % wasformed when the first suspension was added to the second suspension.

Example 28

A positive electrode was prepared in the same manner as in Example 27,except that the aqueous solution was formed by diluting 3.83 g ofammonia solution (28 wt. %) with 3.32 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 5.79 g of deionized water, so that a third suspension with an ammoniaconcentration of 1.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 29

A positive electrode was prepared in the same manner as in Example 27,except that the aqueous solution was formed by diluting 5.1 g of ammoniasolution (28 wt. %) with 4.42 g of deionized water, and the secondsuspension was prepared by mixing the binder and conductive agent in 3.4g of deionized water, so that a third suspension with an ammoniaconcentration of 2 wt. % was formed when the first suspension was addedto the second suspension.

Example 30

A positive electrode was prepared in the same manner as in Example 24,except that the homogenized cathode slurry was coated on an aluminumfoil without a carbon coating.

Comparative Example 4

A positive electrode slurry was prepared by dispersing 47 g of NMC622(obtained from Henan Kelong NewEnergy Co., Ltd., Xinxiang, China), 1.5 gof conductive agent (SuperP; obtained from Timcal Ltd, Bodio,Switzerland) and 10 g of LA138 binder (85% water content; obtained fromChengdu Indigo Power Sources Co., Ltd.) in 18.4 g of deionized waterwhile stirring with an overhead stirrer. The slurry was degassed under apressure of about 10 kPa for 1 hour. Then, the slurry was furtherstirred for about 60 minutes at 25° C. at a speed of 1,200 rpm.

The homogenized cathode slurry was coated onto one side of an aluminumfoil having a thickness of 13 μm as a current collector using a doctorblade coater with a gap width of 45 μm. The coated slurry film on thealuminum foil was dried to form a cathode electrode layer by anelectrically heated conveyor oven (TH-1A, obtained from Nanjing TonghaoDrying Equipment Co. Ltd., China) at 50° C. at a conveyor speed of about5 meters/minute. The drying time was about 6 minutes. The electrode wasthen pressed to decrease the thickness of the cathode electrode layer to35 μm.

Comparative Example 5

A positive electrode was prepared in the same manner as in ComparativeExample 4, except that the homogenized cathode slurry was coated onto analuminum foil with a carbon coating having a thickness of 1 μm.

Comparative Example 6

A positive electrode slurry was prepared by dispersing 47 g of NMC622(obtained from Henan Kelong NewEnergy Co., Ltd., Xinxiang, China), 1.5 gof conductive agent (SuperP; obtained from Timcal Ltd, Bodio,Switzerland) and 15 g of PVDF binder (10 wt. % solution in NMP; Solef®5130, obtained from Solvay S.A., Belgium) in 13.4 g of NMP (≥99%,Sigma-Aldrich, USA) while stirring with an overhead stirrer. The slurrywas degassed under a pressure of about 10 kPa for 1 hour. Then, theslurry was further stirred for about 60 minutes at 25° C. at a speed of1,200 rpm.

The homogenized cathode slurry was coated onto one side of an aluminumfoil having a thickness of 13 μm as a current collector using a doctorblade coater with a gap width of 45 μm. The coated slurry film on thealuminum foil was dried to form a cathode electrode layer by anelectrically heated conveyor oven (TH-1A, obtained from Nanjing TonghaoDrying Equipment Co. Ltd., China) at 50° C. at a conveyor speed of about5 meters/minute. The drying time was about 6 minutes. The electrode wasthen pressed to decrease the thickness of the cathode electrode layer to35 μm.

Comparative Example 7

4.12 g of ammonia solution (28 wt. %) was diluted with 7.42 g deionizedwater to produce an aqueous solution at 25° C. with an ammoniaconcentration of 10 wt. %. After the addition, the aqueous solution wasfurther stirred for about 5 minutes at 25° C. Thereafter, a firstsuspension was prepared by dispersing 47 g of NMC622 (obtained fromHenan Kelong NewEnergy Co., Ltd., Xinxiang, China) in the aqueoussolution at 25° C. The first suspension was sealed and left to rest at25° C. for 30 minutes. The cathode material was then filtered and driedin a box-type resistance oven under vacuum (DZF-6020, obtained fromShenzhen Kejing Star Technology Co. Ltd., China) at 60° C. The dryingtime was about 12 hours.

A positive electrode slurry was prepared by dispersing all of the driedcathode material, 1.5 g of conductive agent (SuperP; obtained fromTimcal Ltd, Bodio, Switzerland) and 10 g of binder (LA138; 85% watercontent, Chengdu Indigo Power Sources Co., Ltd., China) in 26.9 g ofdeionized water (≥99%, Sigma-Aldrich, USA) while stirring with anoverhead stirrer. The slurry was degassed under a pressure of about 10kPa for 1 hour. Then, the slurry was further stirred for about 60minutes at 25° C. at a speed of 1,200 rpm.

The homogenized cathode slurry was coated onto one side of an aluminumfoil having a thickness of 13 μm as a current collector using a doctorblade coater (MSK-AFA-III, obtained from Shenzhen Kejing Star TechnologyLtd., China) with a gap width of 45 μm. The coated film on the aluminumfoil was dried in a box-type resistance oven (DZF-6020, obtained fromShenzhen Kejing Star Technology Co. Ltd., China) at 50° C. The dryingtime was about 6 minutes. The electrode was then pressed to decrease thethickness of the cathode electrode layer to 35 μm.

Comparative Example 8

A positive electrode was prepared in the same manner as in ComparativeExample 7, except that the 10 g of LA138 binder was replaced with 15 gof PVDF (Solef® 5130, obtained from Solvay S.A., Belgium), and the 26.9g of deionized water to form the slurry was replaced with 21.9 g of NMP(≥99%, Sigma-Aldrich, USA).

Preparation of Negative Electrode of Examples 18-30 and ComparativeExamples 4-8

The negative electrodes of Examples 18-30 and Comparative Examples 4-8were prepared in the same manner as in Example 1.

Assembling of Coin Cell of Examples 18-30 and Comparative Examples 4-8

The coin cells of Examples 18-30 and Comparative Examples 4-8 wereassembled in the same manner as in Example 1.

Electrochemical Measurements of Examples 18-30 and Comparative Examples4-8

The electrochemical performance of the coin cells of Examples 18-30 andComparative Examples 4-8 was measured in the same manner as in Example 1and the test results are shown in Table 2 below.

Example 31

A positive electrode was prepared in the same manner as in Example 19,except that the 47 g of NMC622 was replaced with NMC811 of the sameweight, and the 10 g of LA138 binder was replaced with LA133 of the sameweight.

Example 32

A positive electrode was prepared in the same manner as in Example 31,except that the aqueous solution was formed by diluting 4.87 g ofammonia solution (28 wt. %) with 22.4 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 5.14 g of deionized water, so that a third suspension with an ammoniaconcentration of 1.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 33

A positive electrode was prepared in the same manner as in Example 31,except that the aqueous solution was formed by diluting 7.6 g of ammoniasolution (28 wt. %) with 35 g of deionized water, and the secondsuspension was prepared by mixing the binder and conductive agent in5.33 g of deionized water, so that a third suspension with an ammoniaconcentration of 2 wt. % was formed when the first suspension was addedto the second suspension.

Example 34

A positive electrode was prepared in the same manner as in Example 31,except that the aqueous solution had an ammonia concentration of 10 wt.% and was formed by diluting 4 g of ammonia solution (28 wt. %) with 7.2g of deionized water, and the second suspension was prepared by mixingthe binder and conductive agent in 4.93 g of deionized water, so that athird suspension with an ammonia concentration of 1.5 wt. % was formedwhen the first suspension was added to the second suspension.

Example 35

A positive electrode was prepared in the same manner as in Example 34,except that the aqueous solution was formed by diluting 5.67 g ofammonia solution (28 wt. %) with 10.2 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 4.99 g of deionized water, so that a third suspension with an ammoniaconcentration of 2 wt. % was formed when the first suspension was addedto the second suspension.

Example 36

A positive electrode was prepared in the same manner as in Example 34,except that the aqueous solution was formed by diluting 7.44 g ofammonia solution (28 wt. %) with 13.4 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 4 g of deionized water, so that a third suspension with an ammoniaconcentration of 2.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 37

A positive electrode was prepared in the same manner as in Example 34,except that the aqueous solution was formed by diluting 12 g of ammoniasolution (28 wt. %) with 21.6 g of deionized water, and the secondsuspension was prepared by mixing the binder and conductive agent in 4 gof deionized water, so that a third suspension with an ammoniaconcentration of 3.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 38

A positive electrode was prepared in the same manner as in Example 31,except that the aqueous solution had an ammonia concentration of 15 wt.% and was formed by diluting 3.83 g of ammonia solution (28 wt. %) with3.32 g of deionized water, and the second suspension was prepared bymixing the binder and conductive agent in 5.79 g of deionized water, sothat a third suspension with an ammonia concentration of 1.5 wt. % wasformed when the first suspension was added to the second suspension.

Example 39

A positive electrode was prepared in the same manner as in Example 38,except that the aqueous solution was formed by diluting 5.1 g of ammoniasolution (28 wt. %) with 4.42 g of deionized water, and the secondsuspension was prepared by mixing the binder and conductive agent in 3.4g of deionized water, so that a third suspension with an ammoniaconcentration of 2 wt. % was formed when the first suspension was addedto the second suspension.

Example 40

A positive electrode was prepared in the same manner as in Example 38,except that the aqueous solution was formed by diluting 6.66 g ofammonia solution (28 wt. %) with 5.77 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 3.69 g of deionized water, so that a third suspension with an ammoniaconcentration of 2.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 41

A positive electrode was prepared in the same manner as in Example 38,except that the aqueous solution was formed by diluting 8.5 g of ammoniasolution (28 wt. %) with 7.37 g of deionized water, and the secondsuspension was prepared by mixing the binder and conductive agent in4.99 g of deionized water, so that a third suspension with an ammoniaconcentration of 3 wt. % was formed when the first suspension was addedto the second suspension.

Example 42

A positive electrode was prepared in the same manner as in Example 38,except that the aqueous solution was formed by diluting 10.4 g ofammonia solution (28 wt. %) with 9.03 g of deionized water, and thesecond suspension was prepared by mixing the binder and conductive agentin 5.39 g of deionized water, so that a third suspension with an ammoniaconcentration of 3.5 wt. % was formed when the first suspension wasadded to the second suspension.

Example 43

A positive electrode was prepared in the same manner as in Example 35,except that the first suspension was sealed and left to rest for 10minutes.

Example 44

A positive electrode was prepared in the same manner as in Example 35,except that the first suspension was sealed and left to rest for 60minutes.

Example 45

A positive electrode was prepared in the same manner as in Example 35,except that the first suspension was not sealed and left to rest, butactively stirred at 25° C. for 10 minutes with an overhead stirrer at aspeed of 1,200 rpm.

Example 46

A positive electrode slurry was prepared in the same manner as inExample 35, except that the first suspension was not sealed and left torest, but actively stirred at 25° C. for 60 minutes with an overheadstirrer at a speed of 1,200 rpm.

Example 47

A positive electrode slurry was prepared in the same manner as inExample 35, except that the homogenized cathode slurry was coated on analuminum foil without a carbon coating.

Example 48

A positive electrode was prepared in the same manner as in Example 35,except that the 47 g of NMC811 was replaced with NCA of the same weight.

Example 49

A positive electrode was prepared in the same manner as in Example 4,except that the 47 g of NMC532 was replaced with a core-shell cathodeactive material (C-S) comprising NMC532 as the core andLi_(0.95)Ni_(0.53)Mn_(0.29)Co_(0.15)Al_(0.03)O₂ as the shell. Thecathode active material has a particle size D50 of about 35 μm. Thethickness of the shell was about 3 μm.

Example 50

A positive electrode was prepared in the same manner as in Example 4,except that the 47 g of NMC532 was replaced with a core-shell cathodeactive material (C-S) comprising NMC622 as the core andLi_(0.95)Ni_(0.53)Mn_(0.29)Co_(0.15)Al_(0.03)O₂ as the shell. Thecathode active material has a particle size D50 of about 35 μm. Thethickness of the shell was about 3 μm.

Comparative Example 9

A positive electrode slurry was prepared by dispersing 47 g of NMC811(obtained from Henan Kelong NewEnergy Co., Ltd., Xinxiang, China), 1.5 gof conductive agent (SuperP; obtained from Timcal Ltd, Bodio,Switzerland) and 10 g of LA133 binder (85% water content; obtained fromChengdu Indigo Power Sources Co., Ltd.) in 20.9 g of deionized waterwhile stirring with an overhead stirrer. The slurry was degassed under apressure of about 10 kPa for 1 hour. Then, the slurry was furtherstirred for about 60 minutes at 25° C. at a speed of 1,200 rpm.

The homogenized cathode slurry was coated onto one side of an aluminumfoil having a thickness of 13 μm as a current collector using a doctorblade coater with a gap width of 45 μm. The coated slurry film on thealuminum foil was dried to form a cathode electrode layer by anelectrically heated conveyor oven (TH-1A, obtained from Nanjing TonghaoDrying Equipment Co. Ltd., China) at 50° C. at a conveyor speed of about5 meters/minute. The drying time was about 6 minutes. The electrode wasthen pressed to decrease the thickness of the cathode electrode layer to35 μm.

Comparative Example 10

A positive electrode slurry was prepared in the same manner as inComparative Example 9, except that the homogenized cathode slurry wascoated on an aluminum foil with a carbon coating having a thickness of 1μm.

Comparative Example 11

A positive electrode slurry was prepared by dispersing 47 g of NMC811(obtained from Henan Kelong NewEnergy Co., Ltd., Xinxiang, China), 1.5 gof conductive agent (SuperP; obtained from Timcal Ltd, Bodio,Switzerland) and 15 g of PVDF (Solef® 5130, obtained from Solvay S.A.,Belgium) in 15.9 g of NMP (≥99%, Sigma-Aldrich, USA) while stirring withan overhead stirrer. The slurry was degassed under a pressure of about10 kPa for 1 hour. Then, the slurry was further stirred for about 60minutes at 25° C. at a speed of 1,200 rpm.

The homogenized cathode slurry was coated onto one side of an aluminumfoil having a thickness of 13 μm as a current collector using a doctorblade coater with a gap width of 45 μm. The coated slurry film on thealuminum foil was dried to form a cathode electrode layer by anelectrically heated conveyor oven (TH-1A, obtained from Nanjing TonghaoDrying Equipment Co. Ltd., China) at 50° C. at a conveyor speed of about5 meters/minute. The drying time was about 6 minutes. The electrode wasthen pressed to decrease the thickness of the cathode electrode layer to35 μm.

Preparation of Negative Electrode of Examples 31-50 and ComparativeExamples 9-11

The negative electrodes of Examples 31-50 and Comparative Examples 9-11were prepared in the same manner as in Example 1.

Assembling of Coin Cell of Examples 31-50 and Comparative Examples 9-11

The coin cells of Examples 31-50 and Comparative Examples 9-11 wereassembled in the same manner as in Example 1.

Electrochemical Measurements of Examples 31-50 and Comparative Examples9-11

The electrochemical performance of the coin cells of Examples 31-50 andComparative Examples 9-11 was measured in the same manner as in Example1 and the test results are shown in Table 3 below.

TABLE 1 Homogenization of 0.5 C Capacity Aqueous solution Treatment inthird suspension Initial retention Cathode Base first suspension Base pHof discharging after active conc. Temp Time conc. Temp Time cathodeslurry capacity 50 cycles material Base (%) pH (° C.) (mins) Solvent (%)(° C.) (hrs) Beginning End (mAh/g) (%) Example 1 NMC532 NH₃ 5 12.0 25 30Water 0.5 25 1 11.8 11.5 145 83.7 Example 2 NMC532 NH₃ 5 11.9 25 30Water 1 25 1 11.8 11.6 144 83.5 Example 3 NMC532 NH₃ 5 12.0 25 30 Water1.5 25 1 11.9 11.7 147 82.8 Example 4 NMC532 NH₃ 10 12.1 25 30 Water 125 1 12.0 11.7 157 87.9 Example 5 NMC532 NH₃ 10 12.1 25 30 Water 1.5 251 12.0 11.7 152 82.6 Example 6 NMC532 NH₃ 2 11.8 25 30 Water 0.5 25 111.7 11.5 125 80.3 Example 7 NMC532 NH₃ 15 12.3 25 30 Water 1 25 1 12.111.9 147 85.1 Example 8 NMC532 NH₃ 15 12.3 25 30 Water 1.5 25 1 12.211.9 149 82.5 Example 9 NMC532 NH(CH₃)₂ 10 12.1 25 30 Water 1 25 1 11.911.6 147 83.8 Example 10 NMC532 N(CH₃)₃ 10 12.0 25 30 Water 1 25 1 11.911.6 142 85.8 Example 11 NMC532 N(CH₃)₃ 10 12.1 25 30 Water 1.5 25 112.0 11.7 145 83.5 Example 12 NMC532 N(CH₃)₃ 10 12.0 25 30 Water 2 25 111.9 11.6 134 83.6 Example 13 NMC532 NH₃ 10 12.1 25 30 Water 1 25 1 12.011.7 152 84.2 Example 14 NMC532 NH₃ 10 12.1 25 30 Water 1 25 1 11.9 11.7148 83.1 Example 15 NMC532 NH₃ 10 12.0 25 30 Water 1 25 1 11.9 11.6 14982.7 Example 16 NMC532 NH₃ 10 12.1 25 30 Water 1 25 1 11.9 11.6 150 83.7Example 17 NMC532 NH₃ 10 12.1 25 30 Water 1 25 1 12.0 11.7 152 84.3Comparative NMC532 — — — — — Water — 25 1 11.7 11.5 124 80.2 Example 1Comparative NMC532 — — — — — NMP — 25 1 11.7 11.8 158 84.2 Example 2Comparative NMC532 Citric 10 11.0 25 30 Water 1 25 1 10.9 11.1 111 75.3Example 3 acid* *Treated in acid for comparison against treatment inbase

TABLE 2 Homogenization of 0.5 C Capacity Aqueous solution Treatment inthird suspension Initial retention Cathode Base first suspension Base pHof discharging after active conc. Temp Time conc. Temp Time cathodeslurry capacity 50 cycles material Base (%) pH (° C.) (mins) Solvent (%)(° C.) (hrs) Beginning End (mAh/g) (%) Example 18 NMC622 NH₃ 5 12.6 2530 Water 0.5 25 1 12.5 12.2 153 82.3 Example 19 NMC622 NH₃ 5 12.5 25 30Water 1 25 1 12.6 12.3 154 82.7 Example 20 NMC622 NH₃ 5 12.6 25 30 Water1.5 25 1 12.6 12.3 155 83.2 Example 21 NMC622 NH₃ 5 12.6 25 30 Water 225 1 12.7 12.4 156 84.1 Example 22 NMC622 NH₃ 7 12.7 25 30 Water 1.5 251 12.7 12.3 155 87.3 Example 23 NMC622 NH₃ 10 12.8 25 30 Water 1 25 112.6 12.1 155 88.4 Example 24 NMC622 NH₃ 10 12.7 25 30 Water 1.5 25 112.7 12.2 160 95.0 Example 25 NMC622 NH₃ 10 12.8 25 30 Water 2 25 1 12.712.3 154 85.0 Example 26 NMC622 NH₃ 13 12.9 25 30 Water 1.5 25 1 12.712.4 155 86.2 Example 27 NMC622 NH₃ 15 12.9 25 30 Water 1 25 1 12.6 12.3153 83.7 Example 28 NMC622 NH₃ 15 13.0 25 30 Water 1.5 25 1 12.7 12.3155 84.5 Example 29 NMC622 NH₃ 15 13.0 25 30 Water 2 25 1 12.8 12.5 15283.8 Example 30 NMC622 NH₃ 10 12.8 25 30 Water 1.5 25 1 12.7 12.2 15084.7 Comparative NMC622 — — — — — Water — 25 1 12.2 12.2 145 78.8Example 4 Comparative NMC622 — — — — — Water — 25 1 12.1 12.2 154 80.2Example 5 Comparative NMC622 — — — — — NMP — 25 1 12.2 12.5 162 87.3Example 6 Comparative NMC622 NH₃ 10 12.8 25 30 Water — 25 1 12.2 12.5147 80.3 Example 7* Comparative NMC622 NH₃ 10 12.7 25 30 NMP — 25 1 12.312.2 127 74.2 Example 8* *Cathode active material is thoroughly driedafter treatment in base before adding to third suspension

TABLE 3 Homogenization of 0.5 C Capacity Aqueous solution Treatment inthird suspension Initial retention Cathode Base first suspension Base pHof discharging after active conc. Temp Time conc. Temp Time cathodeslurry capacity 50 cycles material Base (%) pH (° C.) (mins) Solvent (%)(° C.) (hrs) Beginning End (mAh/g) (%) Example 31 NMC811 NH₃ 5 13.2 2530 Water 1 25 1 13.1 12.7 172 83.2 Example 32 NMC811 NH₃ 5 13.2 25 30Water 1.5 25 1 13.1 12.8 173 83.7 Example 33 NMC811 NH₃ 5 13.2 25 30Water 2 25 1 13.2 12.7 175 84.2 Example 34 NMC811 NH₃ 10 13.3 25 30Water 1.5 25 1 13.1 12.8 186 88 Example 35 NMC811 NH₃ 10 13.2 25 30Water 2 25 1 13.2 12.9 180 95.7 Example 36 NMC811 NH₃ 10 13.3 25 30Water 2.5 25 1 13.2 12.8 179 88.8 Example 37 NMC811 NH₃ 10 13.3 25 30Water 3.5 25 1 13.3 12.9 176 85.9 Example 38 NMC811 NH₃ 15 13.5 25 30Water 1.5 25 1 13.2 12.9 178 84.8 Example 39 NMC811 NH₃ 15 13.5 25 30Water 2 25 1 13.3 12.9 177 83.9 Example 40 NMC811 NH₃ 15 13.6 25 30Water 2.5 25 1 13.4 12.9 176 85.1 Example 41 NMC811 NH₃ 15 13.7 25 30Water 3 25 1 13.5 13.0 173 85.3 Example 42 NMC811 NH₃ 15 13.6 25 30Water 3.5 25 1 13.5 13.0 175 85.7 Example 43 NMC811 NH₃ 10 13.2 25 10Water 2 25 1 13.2 12.9 178 93.6 Example 44 NMC811 NH₃ 10 13.3 25 60Water 2 25 1 13.3 12.9 179 94.4 Example 45 NMC811 NH₃ 10 13.2 25 10Water 2 25 1 13.3 12.8 183 88.0 Example 46 NMC811 NH₃ 10 13.3 25 60Water 2 25 1 13.2 12.9 181 87.3 Example 47 NMC811 NH₃ 10 13.3 25 30Water 2 25 1 13.2 12.9 163 80.2 Example 48 NCA NH₃ 10 13.1 25 30 Water 225 1 13.0 12.8 178 93.3 Example 49 C-S NH₃ 10 12.2 25 30 Water 1 25 112.0 11.7 153 86.9 Example 50 C-S NH₃ 10 12.3 25 30 Water 1 25 1 12.111.7 155 87.8 Comparative NMC811 — — — — — Water — 25 1 13.2 13.3 16977.3 Example 9 Comparative NMC811 — — — — — Water — 25 1 13.0 13.2 16575.2 Example 10 Comparative NMC811 — — — — — NMP — 25 1 13.2 13.7 18285.7 Example 11

TABLE 4 Undiluted amount Conc. of of Li dissolved % of Li dissolved fromammonia from cathode cathode material relative solution (M) material(ppm)* to pure water treatment 0 35205.768 100.00 2.552 34404.465 97.723.318 32258.222 91.63 3.828 31817.213 90.38 4.338 31160.625 88.51 5.10430619.663 86.97 *Based on total weight of lithium in the cathodematerial added

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. In some embodiments,the methods may include numerous steps not mentioned herein. In otherembodiments, the methods do not include, or are substantially free of,any steps not enumerated herein. Variations and modifications from thedescribed embodiments exist. The appended claims intend to cover allthose modifications and variations as falling within the scope of theinvention.

What is claimed is:
 1. A cathode slurry for a secondary battery,comprising a cathode active material, a binder, a solvent and a basehaving a formula of R¹R²R³N, wherein each of R¹, R² and R³ isindependently H, C₁₋₆ alkyl, C₃₋₆ cycloalkyl, C₁₋₆ heteroalkyl, C₄₋₆cycloalkylalkyl, C₂₋₆ alkoxyalkyl, or C₃₋₆ alkoxyalkoxyalkyl, where theC₁₋₆ alkyl, C₃₋₆ cycloalkyl, C₁₋₆ heteroalkyl, C₄₋₆ cycloalkylalkyl,C₂₋₆ alkoxyalkyl, or C₃₋₆ alkoxyalkoxyalkyl is optionally substitutedwith one or more substituents, where each of the substituents isindependently alkyl or cycloalkyl.
 2. The cathode slurry of claim 1,wherein each of R¹, R² and R³ is independently C₁₋₄ alkyl, C₃₋₅cycloalkyl, C₁₋₄ heteroalkyl, C₂₋₄ alkoxyalkyl, or C₃₋₅alkoxyalkoxyalkyl.
 3. The cathode slurry of claim 1, wherein each of R¹,R² and R³ is independently H, methyl, ethyl, propyl, isopropyl,cyclopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, cyclobutyl,pentyl, methoxymethyl, ethoxymethyl, or methoxyethoxymethyl.
 4. Thecathode slurry of claim 1, wherein the base is selected from the groupconsisting of ammonia, methylamine, ethylamine, propylamine,isopropylamine, cyclopropylamine, butylamine, N-butylamine,tert-butylamine, isobutylamine, sec-butylamine, cyclobutylamine,dimethylamine, N-ethylmethylamine, diethylamine, N-methylpropylamine,N-methylcyclopropanamine, N-ethyl-N-propylamine,N,2-dimethyl-1-propanamine, N-tert-butylmethylamine, diisopropylamine,N-methyl-tert-butylamine, trimethylamine, N,N-dimethylethylamine,N,N-diethylmethylamine, N,N-dimethylisopropylamine, triethylamine andcombinations thereof.
 5. The cathode slurry of claim 1, wherein thecathode active material is selected from the group consisting ofLi_(1+x)Ni_(a)Mn_(b)Co_(c)Al_((1−a−b−c))O₂,LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂, LiNi_(0.4)Mn_(0.4)Co_(0.2)O₂,LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂, LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂,LiNi_(0.7)Mn_(0.15)C_(0.15)O₂, LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂,LiNi_(0.92)Mn_(0.04)Co_(0.04)O₂, LiNi_(0.8)Co_(0.15)Al_(0.05)O₂, LiCoO₂,LiNiO₂, LiMnO₂, LiMn₂O₄, Li₂MnO₃, and combinations thereof, wherein−0.2≤x≤0.2, 0≤a<1, 0≤b<1, 0≤c<1, and a+b+c≤1.
 6. The cathode slurry ofclaim 1, wherein the cathode active material comprises or is acore-shell composite having a core and shell structure, wherein the coreand the shell each independently comprise a lithium transition metaloxide selected from the group consisting ofLi_(1+x)Ni_(a)Mn_(b)Co_(c)Al_((1−a−b−c))O₂, LiCoO₂, LiNiO₂, LiMnO₂,LiMn₂O₄, Li₂MnO₃, LiCrO₂, Li₄Ti₅O₁₂, LiV₂O₅, LiTiS₂, LiMoS₂, andcombinations thereof, wherein −0.2≤x≤0.2, 0≤a<1, 0≤b<1, 0≤c<1, anda+b+c≤1.
 7. The cathode slurry of claim 6, wherein the shell comprises alithium transition metal oxide selected from the group consisting ofLiNi_(0.33)Mn_(0.33)Co_(0.33)O₂, LiNi_(0.4)Mn_(0.4)Co_(0.2)O₂,LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂, LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂,LiNi_(0.7)Mn_(0.15)Co_(0.15)O₂, LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂,LiNi_(0.92)Mn_(0.04)Co_(0.04)O₂, LiNi_(0.8)Co_(0.15)Al_(0.05)O₂, LiNiO₂,and combinations thereof.
 8. The cathode slurry of claim 1, wherein thesolvent is water or a mixture of water and an alcohol.
 9. The cathodeslurry of claim 8, wherein the alcohol is selected from the groupconsisting of ethanol, isopropanol, n-propanol, tert-butanol, n-butanol,and combinations thereof.
 10. The cathode slurry of claim 8, wherein thealcohol comprises from about 1% to about 30% of the total weight of thecathode slurry.
 11. The cathode slurry of claim 1, further comprising aconductive agent that is selected from the group consisting of carbon,carbon black, graphite, expanded graphite, graphene, graphenenanoplatelets, carbon fibers, carbon nano-fibers, graphitized carbonflake, carbon tubes, carbon nanotubes, activated carbon, mesoporouscarbon and combinations thereof.
 12. The cathode slurry of claim 1,wherein the boiling point of the base is lower than 100° C. at apressure of 1 atm.
 13. The cathode slurry of claim 1, wherein theconcentration of the base in the cathode slurry is from about 0.5% toabout 3.5% by weight, based on the total weight of the cathode slurry.14. The cathode slurry of claim 1, wherein the pH of the cathode slurryis from about 8 to about 14, or from about 11 to about 13.5.
 15. Thecathode slurry of claim 1, wherein the binder material is selected fromthe group consisting of styrene-butadiene rubber, carboxymethylcellulose, polyvinylidene fluoride, acrylonitrile copolymer, polyacrylicacid, polyacrylonitrile, poly(vinylidene fluoride)-hexafluoropropene,LA132, LA133, LA138, latex, a salt of alginic acid, and combinationsthereof.
 16. The cathode slurry of claim 15, wherein the salt of alginicacid comprises a cation selected from the group consisting of Na, Li, K,Ca, NH₄, Mg, Al, and combinations thereof.
 17. The cathode slurry ofclaim 1, wherein lithium loss of the cathode active material isinhibited by a percentage from about 1 percent to about 50 percent. 18.The cathode slurry of claim 1, wherein lithium loss of the cathodeactive material is inhibited by a percentage of about 10 percent orabove.
 19. The cathode slurry of claim 1, wherein the solid content ofthe cathode slurry is from about 45% to about 75% by weight, based onthe total weight of the cathode slurry.
 20. The cathode slurry of claim1, wherein the cathode slurry is free of a dispersing agent selectedfrom the group consisting of a cationic surfactant, an anionicsurfactant, a nonionic surfactant, an amphoteric surfactant, and apolymeric acid.